It's more RH than Fedora, meaning the packages will be older. The only real problem I've had is sound on a particular laptop, which I believe is due to an older version of alsa. (I haven't had this problem on my desktop.)
There is a 5.2 live CD that you can try to make sure it works with your hardware.
The forums are far smaller and more serious than Fedora's. (Their forum software is also old, though that's going to be updated sooner or later.)
Intelligent questions are usually answered relatively quickly though. (However, completely beginner questions, showing the user hasn't done any research are either ignored or sent to the various resources. In contrast, Fedora's forums will often start a silly off-topic thread leading to beer. I think it's because the CentOS people tend to be IT professionals and probably older.)
They pay more attention to getting things properly documented than do either Fedora or RedHat. For example, a major change in bind (location of files) wasn't listed in RH's changelog. Someone filed a bug report on RH's horribly slow and cumbersome bugzilla, suggesting that a README.RedHat be included in /usr/share/doc if nowhere else, and the developer said, nah, you've posted it here.
In contrast, CentOS quickly had it in their FAQ.
If the liveCD works with your hardware, I'd say go for it. It's far more stable, there are far fewer updates, and the QA is probably better than RH's and definitely better than Fedora's.
(In fairness, Fedora never claims to be anything else save on its public web pages. However, when people come on the Fedora forums complaining how updates broke something, they're often told, nicely as a rule, that they might be better off using Ubuntu or something similar. We Fedora veterans expect it to break, especially just after a new release.
Some more esoteric packages might be harder to find. You're using different repos, things built for RHEL 5 rather than Fedora--there are a few people, such as Dag Wiers, however, who serve the equivalent of Livna repos, though again, the packages are usually more stable and better tested. Like Debian, they put emphasis on stability rather than having the latest and greatest.
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