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Maybe the Fallout 3 since I bought the game at full price and later purchased each new DLC at full price too. Usually I wait for the GOTY edition, but the game was just too good, I couldn't wait!
My most expensive game bought was probably borderlands 2, I bought the loot case when it first came out, I got all the dlc as it came out, it sent me back quite a bit on cash.
I also bought a claptrap plush toy, a claptrap keyring, and a claptrap phone cover.
Mine was GTA V because I bought it at full price. I usually wait for price slashes because I'm not that excited to play each game as they come out, as I always have a huge backlog still waiting to be finished anyway, but this is one of the games I immediately wanted to see and experience so I paid for it full price instead of waiting for it to be old and discounted.
For me it's Rock Band as I had (I think) all instruments for it and spend some money on some tracks.
Other than that, I've never gotten any special editions on the PS3 so I never spent more than the standard $60.
I think the most expensive PS3 game I have bought was probably GTA V as I bought it on pre-order and because I was living in the United Arab Emirates at the time, they charged me a premium fare. It came to around 80$ for the game, while it was a lot of money, the game truly delivered and was worth all the money I spent.
I think the only game I ever paid the full 60 bucks for was MAG. although it had its issues, I enjoyed the hell out of that game! 256 players on one server was such a blast. The is such an underrated game.
The most expensive game that I have bought for the PlayStation 3 must have been Call of Duty, honestly. Most games that I buy are fairly cheap, but Call of Duty is always really expensive, and I've no idea why, it isn't worth the amount that it is.