Here are some of my tips from my background as a CTO and VP of Engineering in Silicon Valley:
a) It’s clichéd, but one must only hire “A players” to begin with. The initial small team should be comprised completely of rock stars, with lots of specific experience in the domains that they are working in. The early product decisions and product releases are absolutely critical. Being able to release quality product quickly, that performs well, and iterating, is critical.
b) Besides and including the technology team, the most important function in a product development team (this comprises marketing+technology) is product management. Product management defines what iterative releases of the product will have. If we don’t define the target well, we’ll never hit it.
c) I am a big believer in small teams… and continuing to break down teams that grow beyond certain sizes in to bigger numbers of smaller teams. Communication overhead is significant. The mythical person-month is, indeed, mythical.
d) Despite the recommended small teams, in the early days, one should defer any layers of management as long as possible.
e) Creating cool corporate culture and cohesive teams is incredibly important early on (and fostering that as the company grows is also hugely important – just much more difficult). I like to see all-hands meetings (while a small company) on Friday afternoons (or other times that make sense) so that everyone gets to hear what’s happening, and the employees are all properly motivated and aligned.
f) As the company grows, it is important to begin to hire *some* junior people with less experience (still should be super smart, great communicators, team players). Those people can do the tasks that are less exciting / more mundane, and then we start to create a healthy social organism that can, over time, care for, train, and promote some of those junior people to more significant roles.
g) With this type of company I do not believe in outsourcing… overseas development, potentially, partially (can save on cost, among other positive factors) but not outsourced.
h) Believe it or not the #1 thing I looked for in engineers… is communication and teamwork! Especially communication. Not always easy to find in engineers 
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i) I like to give flexibilty to people, but I am not a big believer in people working at home a lot, with only a few exceptions. There is no substitute for in-person collaboration, including as a whole company.
j) Related to the flexiblity that many information workers have and need, I do believe in flex time… people can work any 16 hours of the day they like .
