A CIO is part of the company leadership. His primary duties is to make policies, create organization (i.e., structure the company, at least the part that reports to him), make strategic decisions etc. In a large company, many technical people report directly or indirectly to the CIO; if there are technical problems to solve, he is supposed to hire people to solve those problems, or - more likely -
have his direct reports hire those people.
I would be very wary if a CIO starts fixing technical problems himself. This probably would mean that he has trouble delegating, or trusting his employees.
There may be a phase in a very small company (like 5-10) where you might have some kind of senior technical person who starts to grow into the CIO role. But that should certainly be a path that develops itself (often it is quite obvious who is a good fit for that role and who isn't), and nothing where you start pondering whether you want to become CIO or not out of the blue.