Today I just finished my work on setting up a chroot environment on my system. The result? Instead of relying on 32bit compatability packages to get 32-bit software to run in a 64bit environment, I can just instead run it within a self-contained 32bit environment. No compatability packages, and it's almost like running the software in native 32bit.
The biggest benefit I've seen so far is working audio and video streaming in second life. To get that, I had to run native 64bit versions of omvviewer or meerkat, which had problems with random freezing that didn't exist in the 32bit versions.
The other big benefit I see is being able to run Wine without issues, as it doesn't work as well when run inside of a 64bit environment. In the past, I had done biweekly testing with Elder Scrolls IV, Oblivion, with each new release of Wine. Due to bugs from running 32bit Wine under a 64bit system, I couldn't do any testing. Now that I have a chroot environment, I can run Wine without problems and can continue testing.
EDIT: Well, wine is unusable in the chroot environment. On the other hand, after clearing my .wine directory and starting from scratch, Oblivion has stopped crashing after the opening movie, so I should be able to resume testing now.