That's definitely a good idea. It helps get a feel of the company without spending a dime yet. However, "company" is a bit much, because you're really dealing with one out of possible hundreds of techs. Also, live chat is mostly manned by level 1 techs. Some of them may be bright individuals, but they still have a lot to learn. Steve Jobs may not be around anymore, but you still wouldn't talk to any Apple employee and judge the company based on that.
Many providers also offer live chat now so it is relatively easy to ask support and customer service a few questions that may be more telling than reviews.