I can see a bootstrapped company using CentOS, or a company running on angel/seed money. Once a company gets Series A funding though, you have to start wondering why they wouldn't upgrade to Red Hat. The message from the company basically is they'd prefer the sysadmin to spend their nights and weekends figuring out problems, instead of making a small payment for support service. This is the type of position you want to run, not walk from.
On a job interview, a good question for a sysadmin to ask an interviewer when they say "do you have any questions to ask me?", is, "Will I support any machines, operating systems or applications that are not under a vendor support contract?" Inevitably there will be one or two legacy machines or applications, but if you get a laundry list in response, run.