Deportivo La Coruna came from two goals down to claim a point in a thrilling 3-3 draw at the Mestalla.
Roberto Soldado had fired Valencia into an early 2-0 lead as he was twice brilliantly set up by Jonas, but Depor halved the deficit when Abel Aguilar bundled home from a corner seven minutes before half-time.
Sofiane Feghouli restored the hosts' two-goal lead before half-time with another wonderful finish from Dani Parejo's pass.
However, the visitors had much the better of the play after the break and after Aguilar had stroked home his second of the night, Pizzi equalised from the penalty spot as Ricardo Costa saw a second yellow card for barging into Riki.
Depor announced their return to the Primera Division with a 2-0 win over Osasuna on Monday night, but it was the hosts who seemed destined to get their first win on the board after some scintillating football saw them score twice in the first 28 minutes.
Firstly, Jonas released Soldado in behind the defence to round Daniel Aranzubia and slot home, before an early contender for goal of the season made it 2-0 as Tino Costa's pass was controlled on the volley by Jonas for Soldado to bicycle-kick the ball into the empty net.
Deportivo responded well and after Riki had a goal ruled out for a marginal offside decision, Aguilar prodded home after Valencia failed to clear Bruno Gama's corner.
However, the hosts soon had a third goal as substitute Parejo's pass freed Feghouli down the right and his low shot across Aranzubia arrowed into the net.
The Depor goalkeeper though made a vitally important save to deny Soldado a hat-trick seconds before half-time and Valencia never recovered the same fluidity after the break.
Aguilar coolly slotted home just before the hour mark from Aythami's cut-back, and with Jose Luis Oltra's side piling on the pressure, 15 minutes later Costa was harshly given his marching orders for a push on Riki inside the area.
Pizzi sent Diego Alves the wrong way from the spot, but Valencia were thankful to the Brazilian for saving them a point in stoppage time when Gama cut inside and fired a shot low to Alves' left which he did well to parry.