Perhaps give them some flexibility if there's a technical co-founder as CTO.
It depends on what the startup is working on. If it's trying to sell into the enterprise I'd be a lot more confident in its future if the CEO is heavily sales-focused provided there's also a technical co-founder keeping things sane on the tech side.
That's what I thought. I thought that the character of one would balance the other out in this case. (Not that there is any guarantee, of course.) I was wrong.