Unless you are going to be a direct report (short- and long-term) to the CEO, specific situational/tactical questions aren't going to be of much value since your manager (either existing or TBD), rather than the CEO, is going to be making most of the decisions that directly impact you day-to-day. I'd be asking more open-ended 'big picture' questions about things I cared about at a strategic level (how are they funded and is there an eventual exit strategy and if so what is it[1], overall product/services direction, who they view as their primary customers/competitors, short and long term challenges to survival and growth, how do they see me helping them get where they're going etc) and see where they go with them.[2] Ask followups that try to get them to elaborate but not necessarily challenge the previous answer(s)... you want to get their views even if they conflict with yours. You are not trying to change their mind or show them how smart you are. (if you ask intelligent questions well, a good CEO will notice)

You're likely to get better answers if you've done at least a bit of homework about the company and space they're in and ask specific and relevant, rather than generic checklist questions. Let's say it's a small 10-person company... they probably don't have any managers yet. So then you'd probably want to ask some questions to get a feel for how the CEO views management and what makes a good manager to try to sense of how that's likely to evolve. If they're a 100-person company, that question has already been answered: you should be talking to a couple of the managers during the interview process and get your feel for management and their priorities from them. Essentially, try to ask the CEO the questions you can't get answers to by talking to other people and/or observing the environment since who and what's already there tells you more than the CEO's answers would.

[1] Sure, funding/exit strategy questions matter from an economic evaluation of what the best case financial end-game is for you. But it also tells you a great deal about what life is going to be like while you work towards it. Your experience at a 10-person company that is self-funded and profitable is likely to be very different than one that is VC funded but identical in every other way. For example, a self-funded startup (more likely to just be a small, rapidly-growing business) there may be no exit strategy and that can be a good thing from a quality of life standpoint.

[2] Keep in mind that a lot of the answers you will get to these types questions will at best be aspirational and at worst be canned responses. Six months later, business realities might require changing direction and invalidating them anyway. That's why I wouldn't care too much about the specific answers (unless they are commitments to you that they are willing to put in writing), but rather the sense you get of the person and where they decide to go with the answers. Does the discussion seem casual and natural or formal and forced? What are their priorities and did they seem cagey, sincere, controlling, on a mission, narcissistic, driven etc... these indirect answers will help paint a picture of what you can expect your life at that company to be like and whether or not you think the CEO has the traits needed to actually pull it off. If you get no sense of the person and/or everything sounds too perfect/generic/canned/polished/politically correct... I'd take that as a red flag.