It was Deportivo who started the better of the two sides and the visitors were ahead in the 13th minute when Bruno Gama fired the ball powerfully past Robert Gago in the Zaragoza goal.
Riki doubled his side's lead midway through the first period by finding space in the box before calmly slotting the ball into the bottom corner.
Zaragoza pulled a goal back before the break through Apono, who was able to emphatically convert a penalty after Tiago Pinto was adjudged to have handled inside the area.
The game turned on a crucial decision just after the interval when Pizzi was given a second yellow card for a late tackle on Francisco Montanes.
It was Montanes who equalised on the hour mark as he latched onto a loose ball to rifle the ball in from 12 yards.
Alvaro Gonzalez put Zaragoza ahead just three minutes later, meeting Victor Rodriguez's corner with a perfectly timed header.
Helder Postiga wrapped up the victory for the hosts in the closing stages by twice beating Daniel Aranzubia with close range headers.
There was still time for Bodipo to head home a consolation goal but Zaragoza ended the match as comfortable winners.