It depends on the team.
If your product and sales DNA is very enterprise, you’ll have a lot easier time convincing a handful of Fortune 500 customers to write you six figure checks to get going.
If your product and sales DNA is freemium / product-y, you need to start there.
Play to your strengths. So many things are already going against you in a startup, that you need to sell where and how you know how to sell. At least in the early and medium days.