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Ok consider a game where every available quest, except for watcher's keep, is done in chapters 2 and 3 (only 1 stronghold). The long route to the underdark in chapter 4 (sahuagin city) is taken. All three dungeons in the underdark are completely cleared. All the new areas are explored and Watcher's keep is done in chapter 6. The game is then played to the end of ToB. The object really is to get as much EXP as possible.

The question is this, in the above game, when would characters reach 6000000 (six million) EXP. I'd like to know for parties of both four and six.

Not sure for a party of 4, but for a soloing character I tend to hit the XP cap in the Sahuagin City, or in the early stages of the Underdark. With parties of 6 I tend to finish ToB with around 6.5 Million XP each IIRC, so 6 million will be very close to the end of the game...

I almost always play with a party of 6, and we tend to hit 4 million around the end of SoA, with Watcher's Keep left until ToB, so if you do Watcher's Keep in Chapter 6, you should probably hit 6 million soon after leaving Saradush.

But it's really all a question of how far you're willing to go to wring as much EXP out of the game as possible. For instance, In Chapter 6, Ribald has an infinite (or at least close enough) amount of Freedom scrolls, so if you're willing to abuse the scribe-erase-rescribe cheese, that's 9000EXP for the low low price of around 150 gold, as many times as you want. If you don't want to be that cheesy, just sleep during the day, spending your nights walking around whacking the guys from Improved City Encounters for 36,000 EXP every night. Etc.