I've been using coconut fiber/cocopeat as substrate for nearly a year now, and I haven't had any problems with it. Like alittleFREE said, it depends on the type of cocofiber. I use the type that's unfiltered and actually has fibers in it, and not just the shavings that look like dirt. I will say though that it really depends on your local climate and conditions if you want to use it for substrate. I live in Indonesia, and the humidity and ambient temperature here is really similar to the recommended humidity and temperature for optimal ball python care, and since coconut fiber does a really good job at maintaining humidity, I haven't had problems with it. However, if you happen to live in a very humid area, then I really wouldn't use it if I were you. I've also had my BP ingest quite a bit of it on multiple occasions, and she's completely fine right now, so it's not lethal if ingested
TL;DR - Coconut fiber is completely fine in my experience, but the usage depends on your local climate and conditions.