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Blue will always be my favorite.
He showed up the perfect amount of times in the series and was always a challenge. That and being the League champion really helps him. (Yes, I kinda have my Genwunner goggles on, but fuck off)
Silver was also a fantastic rival. Every time you saw him, you knew a fantastic battle was coming.
Barry was the first (and last) rival that felt like a rival after gen II. May battles you like twice with a shit team for fun. Wally was a cunt and I'll never consider him the gen III rival.
Gen VI you're on a team and every battle is just like a "Hey, let me see your team"
>tl:dr Barry is a boss ass bitch and easily in my top fav