The Spanish keeper had the fate of the third round replay in his hands before scoring against compatriot Joel Robles to give West Ham a 9-8 penalty shootout victory after a superb end-to-end thriller ended 2-2 after extra time on Tuesday.
Robles had failed to beat Adrian when he struck the bar with the preceding penalty, leaving the scores level at 8-8 before the West Ham keeper slotted home the 20th penalty of the night.
The Spaniard was so confident he was going to score, he took his gloves off as he prepared for his kick.
"I didn't have any nerves," he told reporters. "I thought 'I'll take off my gloves, this game is over' and I struck the ball.
"It was an unbelievable game and I feel really happy. Joel made some unbelievable saves for Everton but we played well and deserved it in the end.
"I took my gloves off so quickly as I worried that the referee might blow his whistle and book me for time-wasting.
"I have celebrated my saves before, but never scoring a goal. It was my first goal in my career and it's an amazing day."
West Ham next play at League One (third tier) Bristol City in the fourth round after coming through what could be one of the last FA Cup matches played at the Boleyn Ground ahead of their move to the Olympic Stadium at the end of next season.
In an exhilarating match worthy of any swan song, West Ham went ahead when Enner Valencia beat Robles with an angled shot after 51 minutes.
Everton then had Aiden McGeady sent off for a second yellow card four minutes later but the 10 men equalised when Kevin Mirallas struck with a stunning free-kick after 82 minutes.
Romelu Lukaku put Everton 2-1 ahead in the seventh minute of extra time, before substitute Carlton Cole equalised with his first touch in the 113th minute.
The momentum then swung in West Ham's favour in the shootout when Steven Naismith missed Everton's second penalty but with the scores at 4-4, Robles saved Stewart Downing's potential match-winning spot kick.
The next four penalties were converted before Robles cracked his effort against the bar, allowing Adrian to throw down his gauntlets and win it for West Ham.
(Reporting by Mike Collett; Editing by John O'Brien)
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