This is one of those topics that no one likes to talk about when starting a company. Many times it creates tensions between co-founders and many other times the members don't fit their roles correctly, which could lead to trouble down the road. So finding your proper role in your company is something that should not be overlooked.
The trouble with roles is that many times, one will outweigh another. For example, a CxO will outweigh a VP. And a VP will outweigh a lead anything. But it doesn't have to, and that's an important realization to make. Titles are a general guideline to the work that you will be doing, and should not have much else to do with who is superior and who gets paid what.
And if you wan't proof of that. Go get an amazing lead engineer, have him work for you for a year, and then fire them. You won't have a very pleasant time afterwards. You may have been the CTO, but that person built your entire stack.
Feel it out and have fun with it. If you take it serious, then that's the tone that will be set for your company. Try out a role that you are comfortable with. If you're more dev oriented, then steer towards that direction. If you don't really enjoy code, but enjoy organization, then maybe VP or CO will be more up your alley.
Some roles naturally make themselves. For example, the person with a degree in data science, will more than likely be in charge of your data. The ones with the most development experience will more than likely be involved in the tech stack in some shape way or form.
Roles can change early on
If your lead designer is managing 9 people, customer support, ordering equipment, etc, and it's all going down without a hiccup, then he should not be your lead designer. The beauty of roles is that they can change. Preferably early on as oppose to when you're well funded and such.
If the meetings and paperwork are not the ideal scenario that you envisioned when becoming a CFO, then take a step back and find your sweet spot. Nobody should spend their days doing work that they can't stand, and likewise, a company won't grow if their members are unhappy and stressed out.
Let the roles make themselves
There's no such thing as a good VP of technology or a solid CTO. The tasks for those jobs are not really defined. A CTO for example started his career usually as a developer of some type. Then maybe a manager. Then maybe a VP. Now he's the CTO of a company and he has to work with the current roles in order to help define their own.
They work with the current team and management group in order to take the company to the next phase. As current CTO of Renly, my day to day is different each and every day. There's meetings to be had and technology to be implemented and tasks to be organized and such. And in the middle of that, whatever else one can do to help. It's not programming, which is what I've worked on for the past decade, but it's the next phase for sure.
Slowly one begins to settle into the role. It's a bit daunting at first and nerve racking but the more relaxed you remain, the easier the work becomes and the more you can benefit your entire team. But if you panic at any point, then everyone begins to panic. And soon after things begin to collapse. So just roll with the punches. If you get a call about a server going down, you call right back and you settle it then and there. If your tech costs are not maintainable then you make some calls and get to work.
Whatever your role, do it well, do it often and have fun with it.