It's a chance for you to meet the actual CEO (or VP or whatever in a larger company), and also for them to get to meet you in advance, instead of effectively getting "blindsided" by a new person (to exaggerate a bit).
Usually, by the time you've gotten to that point, the decision to hire you has well and truly been made. I don't know what then would need to happen for the actually rather secondary function of giving the CEO the opportunity to veto to become relevant. I'd be curious hearing about anyone who's ever experienced it (on whatever side). I guess it can be a safeguard against vastly unaligned values, but I suspect it's very rare.
But primarily, and effectively, it's usually just a meet-and-greet. And it's hard for me to blame a CEO (or VP etc.) for at least getting to anyone who's going to enter a mutual contract to effectively become part of their company.
(PS: if you find reasons to suspect the CEO isn't delegating effectively to managers, then ask the CEO an open-ended question "How much do you do yourself vs which tasks do you delegate to your managers?" then listen carefully to their answer. And it's still not necessarily a red flag, it may just be a new or inexperienced CEO, or maybe overcompensating for one or two bad hire experiences at current or previous company. Compare to their answer to "How do you assess new hires within the first 90 days?").
The only (minor) negative I'd take from this is that it still behaves like a small startup scaling quickly, and they haven't yet figured out how to to scale interviewing and hiring for when they get larger... but that's overall a good complaint, it shows they're still growing. It's much better that your signoff interview is with the CXO (or VP) than the Director of HR, or an AI bot. Honestly I'd pay more attention to how many days/weeks/months it takes them to make the hiring decision than how many management layers were involved; that's a bigger tell of organizational dysfunction.
Don't overthink.
I've worked for companies that did this, in fact I'd say this is commonplace at startups and small companies, at least till around 500 employees or so. If I ever start another company, I'd operate the same way as a founder/ceo. While Dunbar's Number probably puts an upper limit on the number of people I can truly know in my organization, I think it's incredibly important as a leader to have the possibility of putting a face to a name inside the one endeavor (company) you are wholly responsible for. That doesn't say anything about my trust or lack there-of in the people below me on the org chart.
I almost feel the opposite. I've turned down jobs because I want to understand the strategic direction and the folks I was interviewing with couldn't adequately explain it and they were unwilling to let me meet the folks high enough up the chain that they could as part of my interview process. If I can't get the time of day out of the founder during one of the most important decisions (hiring) that their company makes, they're certainly not going to give me the time of day once I'm in the door and that means I have effectively no feedback mechanism. Why would I want to work there?
Sadly, their CEO has veto-ed every single full time hire they've tried to bring on for past 2 years now.
The only time a CEO should be meeting a hire is if the company is a tiny startup, or the role will be working regularly and directly with the CEO.
Otherwise, it's the worse kind of micromanagement. If the CEO wants to meet the new face they do so after the person starts, and this is the norm outside of tech.