The Ph.D. will always be there, but the opportunity for a startup might disappear with time. Given that, staying upwind ( http://paulgraham.com/hs.html ) would tend to dictate going with a startup.
Not sure I agree with that; I would suggest that the opposite is true. Top-tier PhD programs almost never allow students to defer an acceptance offer, so the person in question would need to re-apply. Being accepted becomes substantially more difficult the longer you've been working in industry, particularly if you haven't been working in something directly related to the PhD's field of study (like a startup). Startu…
At least in CS, all the top schools I'm aware of usually allow you to defer an acceptance offer (IIRC 6 months for MIT, 1 year for Stanford/Berkeley/etc.).