Pizzi was appointed at the Mestalla in December and saw his players run out 2-0 winners over Levante on Saturday in his first match, thanks to goals from Pablo Piatti and Sofiane Feghouli.
However, Valencia are likely to face a much tougher test when cup holders Atletico come to town in the last 16 on Tuesday, with Diego Simeone's men having won their last five league matches.
Atletico's impressive form so far this campaign has seen them match La Liga champions Barcelona point for point, with only goal difference separating the two at the top of the table. Atletico also beat Valencia 3-0 just last month.
The two will do battle for the chance to face Real Betis or Athletic Bilbao in the quarter-finals with the pair due to meet in the first leg at the Estadio Benito Villamarin on Wednesday.
Last season's beaten finalists Real Madrid will be eager to ensure they go one step further this year and clinch the trophy for the first time since 2011, but will need to negotiate a last-16 clash with Osasuna first, with the first leg on Thursday.
While Carlo Ancelotti's side will be overwhelming favourites to seize the initiative at the Bernabeu, Osasuna clinched an important 1-0 win against Espanyol in La Liga on Sunday and also held Real in a 2-2 draw last month.
Real needed an 80th-minute Pepe goal to snatch a point at the Estadio El Sadar and will hope for a more convincing performance this time around.
Barcelona will likely be without the recovering Lionel Messi for the visit of Getafe, a side they have beaten on their last four encounters while scoring 19 times. Local rivals Espanyol travel to second-tier outfit Alcorcon earlier on Wednesday.
Segunda B Group 1 leaders Racing Santander will look to make home advantage count in their first leg against Almeria, who despite their lowly league position have picked up their form of late.
Francisco Javier Rodriguez Vilchez's men are three unbeaten in the league, a run they continued with Saturday's 3-0 victory over Granada.
Elsewhere, on Thursday, Rayo Vallecano will look to the cup to provide a boost to their dismal league form when they host Levante, while Real Sociedad entertain La Liga rivals Villarreal in the day's early kick-off.
