Bosnia-Herzegovina will play in a World Cup for the first time in their history after sealing qualification, while Spain confirmed top spot in Group I ahead of France and Russia condemned Portugal to the playoffs.
Eighteen years after playing their maiden international match, Bosnia-Herzegovina secured their place at the World Cup by beating Lithuania 1-0.
Vedad Ibisevic was their hero, the Stuttgart striker scoring midway through the second half after 67 minutes of tension, and they held on for the three points they needed to finish top.
Greece had to better Bosnia’s result, and their 2-0 victory at home to Liechtenstein proved to be in vain.
World champions Spain finished top of Group I with a 2-0 win at home to Georgia.
Alvaro Negredo and Juan Mata were the scorers for the Spanish, who pipped France to the automatic World Cup spot.
Les Bleus go into the playoffs after ending their group campaign with a 3-0 victory over Finland thanks to goals from Franck Ribery, Joona Toivio (own goal) and Karim Benzema .
Russia secured their place in dramatic circumstances after conceding a last-minute equaliser in a 1-1 draw against Azerbaijan.
Fabio Capello's men began the day three points clear of second-placed Portugal and needing a draw in Baku to ensure they would be on the plane to Brazil.
Roman Shirokov set Russia on their way after 16 minutes, and a win looked even more likely when Maksim Medvedev was sent off for the home side after 73 minutes -- but Vagif Javadov's last-minute strike set nerves fluttering before the visitors held on for the result they wanted.
Portugal secured second place and a playoff spot after they beat ten-man Luxembourg 3-0.
Silvestre Varela put them ahead on the half-hour mark, two minutes after Aurelien Joachim had been sent off for the visitors. Nani added the second in the 36th minute before Helder Postiga seal the win, but Portugal's place in Brazil now depends on them winning a two-legged playoff against another second-placed team.
In the same group, Steven Davis' second-half strike ensured Northern Ireland's disappointing campaign ended on something of a positive note with a battling 1-1 draw in Israel.
England are also heading to Brazil after strikes from Wayne Rooney and Steven Gerrard earned them a 2-0 win over Poland at Wembley.
Ukraine had to settle for second spot in Group H despite an 8-0 demolition of San Marino. Marko Devic grabbed a hat-trick for the visitors with Yevhen Seleznyov (two), Andriy Yarmolenko, Roman Bezus and Vitaliy Mandzyuk also on the scoresheet.
Moldova rounded off their campaign with a 5-2 success in Montenegro.
Alexandr Antoniuc scored twice for the visitors, with Igor Armas, Eugen Sidorenco and Artur Ionita also on target. Stevan Jovetic grabbed both of Montenegro's goals.
Croatia sealed the last playoff spot on offer even though they fell to a 2-0 loss in Scotland in Group A.
Robert Snodgrass and Steven Naismith were the heroes for the home side, but Croatia's earlier efforts in the group stage ensured they finished among the top eight second-placed teams.
Denmark were the side to miss out on the playoffs, finishing second in Group B with a 6-0 rout of Malta courtesy of goals from Morten Rasmussen (two), Daniel Agger (two), Andreas Bjelland and Bille Nielsen.
The Danes pipped Czech Republic to second spot, although Borek Dockal's strike ensured the Czechs completed their campaign with a 1-0 win at home to Bulgaria.
Group B winners Italy were held to a 2-2 draw by Armenia. Alessandro Florenzi and Mario Balotelli were on target for the Azzuri, with Yura Movsisyan and Henrikh Mkhitaryan replying for the visitors.
Belgium were also denied a winning end to their successful Group A campaign as they played out a 1-1 draw with Wales. Kevin De Bruyne gave the hosts a 65th-minute lead, but that was cancelled out by Aaron Ramsey.
Serbia were emphatic 5-1 winners over Macedonia, with goals from Stefan Ristovski (own goal), Dusan Basta, Aleksandr Kolarov, Dusan Tadic and Stefan Scepovic. Macedonia's consolation came from Adis Jahovic.
Group C had already been decided before the final round of fixtures, with winners Germany coming away from second-placed Sweden with a 5-3 victory.
Andre Schurrle's hat-trick formed the backbone of Germany's victory, with Mesut Ozil and Mario Gotze also chipping in. Tobias Hysen netted twice for the hosts, with Alex Kacaniklic adding another.
Andreas Ivanschitz, Sebastien Prodl and David Alaba were the scorers as Austria beat Faroe Islands 3-0.
Republic of Ireland hit back from Dmitry Shomko's opener to see off Kazakhstan 3-1 in Dublin. Robbie Keane and John O'Shea turned things around for the Irish before a late own goal from Andrey Finonchenko rounded the win off.
In Group D, Romania beat off competition from Turkey and Hungary to finish second and bag a playoff place.
Romania’s 2-0 victory over Estonia, courtesy of two goals from Ciprian Marica, saw the Romanians finish two points clear of Hungary, who were also 2-0 winners over Andorra, thanks to Nermanja Nikolic's header and an Ildefons Lima own goal.
Turkey's hopes of finishing as runners-up were ended by a 2-0 loss to Netherlands, for whom Arjen Robben and Wesley Sneijder were the scorers.
Iceland will also have another shot at reaching Brazil 2014 as they claimed second place in Group E with a 1-1 draw in Norway.
The visitors led through Kolbeinn Sigthorsson's 13th-minute strike, and although Daniel Braaten levelled things up on the half hour, the point was enough to see Iceland through ahead of Slovenia, who lost 1-0 in Switzerland.
Granit Xhaka scored the only goal in that match after 74 minutes for a Swiss side who had already won the group.
Cyprus and Albania's World Cup qualification campaigns ended with a whimper as they played out a listless goalless draw in Tuesday's Group E match in Nicosia.
A last-minute goal from Renars Rode saw Latvia snatch a 2-2 draw at home to Slovakia in their final Group G qualifier.
Information from the Press Association was used in this report.