If you start a business and have majority ownership you can always be CEO, but CEO's not for everyone. You can most definitely read books on leadership, charisma, networking, etc, and go act out the role for a while if you're motivated enough. However if you're really a private-type technical person at heart, amazingly once you can afford to hire someone else to do that job (without losing your majority status) you may suddenly find that you don't want it anymore. If that's the case it will probably be better for your company too. Some engineers make great CEO's of course.