Wow so many moments to pick from I first saw ECW in late 99 when I borrowed Living Dangerously 1999 from a mate of mind, then saw pretty much everything until it's dying day, whilst also retrospectively picking up most of the major ECW arena shows from the start.
Things like Sandman's return at the ECW Arena and Raven's return on the night the Dudleys left are two of the most insane pops I have ever heard as a fan, for entirely different reasons. Sandman's return was like the return of the biggest thing ever, whilst Raven was the return of the thing the fans hated the most, but loved that he was back so they could hate him again. Not to mention the fact both guys chose ECW over staying with WCW.
Top moments elsewhere for me though...
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Obviously I never saw this in real time, only viewing in retrospect and it is just everything I loved about Brian Pillman as a perfomer he is so captivating, you hang on his every word. The fans want to love him, he just wants to be hated though. Not hated though in the bog standard heel way, he frays the lines of good and bad so majestically. From referencing his last WCW angle, to the smart marks, to wanting to piss openly in the ECW Arena then you get the backstage stuff involved. Nothing has been done like this before or since, even watching it now it's hard to fathom the brilliance of the sequence of events and how it unfolds.
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The Barely Legal World Title match, I'm a huge Funk fan, a huge Raven fan, the first time I ever saw Barely Legal I never knew what happened, I was living every moment as it if it was happening live. There's so much emotion from the beating he took in the 3 way, the emotion of Tommy Dreamer on commentary wanting to help his mentor, then Funk just making people believe the impossible can happen.