If it's a small startup and you're experienced (or even not) contact the founding team directly and ask for a 30 minute chat with them. There's a good chance you'll be ignored but it tells you what you need to know about the company. If it's a three person company and an interesting person reaches out (and the need someone), guaranteed they'll talk to you unless they're some bureaucracy obsessed weirdos you don't want to get stuck with anyway.