Greetingz!
Well, I've had sketchy experiences with WINE. The project is awesome and I really admire those guys for what they've accomplished thusfar. However, I wouldn't subject someone else to the woes of WINE. That being said;
1) If this is just for you to use, go for it! Can't hurt to learn about it.
2) But if this is for someone else to use, setup Windows in a VM (like VMware Server, it's free), and give them that to play with.
As for the CentOS-ness keeping it's RHEL-ness, well, if you install 3rd-party RPMs, technically you should be "okay". Just dont go replacing things like the Kernel & PERL.
Just my USD $0.02!