A Ph.D. is a huge opportunity cost with an extraordinarily high risk/reward ratio. I have often had undergraduates ask me if they should pursue a Ph.D. I first ask them if it is their desire to teach at a research university. This desire is a little like becoming an NBA player especially in certain technical fields like physics. A horde of Ph.D. candidates is good for tenured Professors and research universities, but not necessarily for the students. Post-doc hell is left as an excercise for the reader.
If they don't have a burning desire to be a professor or happen to dislike trees, I don't really see the point of a Ph.D. I tell them to at least take a hard look at the costs of their decision either way: real financial, opportunity, time, etc. An objective tally will rarely be in favor of a Ph.D.
If you look at hardware, you really need a Ph.D. to make a serious contribution to theory, and a lot of important founders (Intel springs to mind) had doctorates.
My conclusion is that Marc is being a bit sloppy here. Like 75% of the Y Combinator partners, I have a Ph.D.---and I think graduate (and, indeed, undergraduate) degrees are overrated. But given the small percentage of Ph.D.s even among technical people, it would be very surprising if most people having a high impact had them. More relevant is to ask whether Ph.D.s have relatively more impact than those without doctoral degrees. I don't know the answer, but I think it's a more interesting question.