During a mass break out attempt on the Raft Luke Cage vs Purple Man, who has beaten teams of Avengers before.
John Walker, former US Agent, had recently had his left arm and leg amputated. He is assigned as warden of The Raft, a prison for super-criminals. One issue has a black out that results in some of the convicts being released from their cells. Finding himself cornered and threatened, John leaps out of his chair and lays some serious hurt on the first cons to come near him, and even rips some guy's eye out using his metal hook. The fight ends with John (who, remember, is one legged) standing steadily over the knocked out body of a prisoner, daring anyone to start some shit. None rise to the occasion.
Best part, the rest of the prisoners bring him his chair afterwards.
He later catches three prisoners wandering around, making fun of Gunna. He gives them extra work to do as punishment as they sheepishly leave, one saying "Yes, sir. Thank you, sir."
John was offered high-tech prosthetics, which would have enabled him to be back in battle immediately. He instead chose to use the level of tech given to regular soldiers.
The team end up on a mission with Hyperion and the entire issue deals with fighting him. Hyperion is basically an evil expy of Superman, with everything that implies. He regards the other Thunderbolts as completely worthless, especially Ghost, and proceeds to burn Man-Thing, break Juggernaut's legs, and drown Moonstone. He's later beaten up by Juggernaut (and actually breaks his hand trying to cave Juggs' head in), blasted by Moonstone, paralyzed by Ghost, and, after a good Curb-Stomp Battle on him, burned by Man-Thing.
Moonstone: "Coward. Can't have one of these on the team. You shouldn't know fear, Hyperion. Because. Whoever knows fear..."
Juggernaut: "...burns at the touch of the Man-Thing."
On another level, the fact that Marvel kept the team's secret under wraps until the end of the first issue. Even when you know the truth and you're re-reading it all these years later, the revelation that they're the Masters of Evil—and all that entails—still really hits you.
It was considered a CMOA even back then. The first issue of the series was put into a trade with the issue of the team's first appearance due to fan request.
Quicksilver gets one at the end of the Siege event. 'Perfect warrior' Mr. X has just gotten hold of 'ultimate weapon' Gungnir, and bear in mind this is a guy who killed a god before he got his hands on the Spear of Heaven. Quicksilver deals him a Curb-Stomp Battle without pausing for breath:
"I read your dossier as I crossed the ocean. You have supreme fighting skill. I'm actually not that great a fighter. You have the weapon of Odin the All-Father. I have some pieces of iron debris I found lying nearby. You're a mutant, too. You can read minds enough to predict any attack your opponent will make."
"So you will be able to (breaks elbow) anticipate every move I make (breaks wrist) and do absolutely (breaks jaw) nothing about it (breaks hand) because I (breaks other hand) am (breaks ribs) the (breaks knee) fastest (breaks other knee) man (breaks leg) on (knockout blow) Earth."
Whilst we're talking about Siege, Amadeus Cho got a really good one against Mr. X. Mr. X can read minds so that he knows how someone is going to attack him. What does Amadeus do? He throws arrows at Mr. X, doing complicated calculations so that they'll hit him in just the right spots. The best bit of it is that Mr. X can still read Amadeus's mind, he just can't understand the calculations.