Heading into the competition all eyes were on Russian Plushenko in his eleventh European Championships campaign – having racked up seven golds and three silvers to date.
But while Plushenko could only manage sixth Amodio took full advantage as he skated a season's-best short program to sit top of the leaderboard.
Amodio skated clean on his way to scoring 89.82 points, with Spain's Javier Fernandez 1.02 further back in second and France's Brian Joubert currently in third on 83.93.
Great Britain's hopes were dashed as Harry Mattick could only manage 48.08 points and failed to make it to the free skate as he finished 27th with the top 24 progressing.
But all thoughts were with seven-time winner Plushenko, who was failing to find the answers for his disappointing performance.
"I don't understand what happened," said Plushenko. "I probably rushed it going into the triple axel, and I wanted to get the program over with as soon as possible."
"It's unforgivable for me that I fell on the axel. It seems I didn't readjust sufficiently from the routine with the quad to the routine without the quad."