Nanotechnology is frequently heralded as the next wave of technological advance, poised to enable radical innovation across many industries. But as yet little is known about how firms will ultimately create that value. We do know that nanotechnology is based on process innovation, a category of innovation less well understood than product innovation. And we know that new ventures are an important vehicle for commercializing radical technology. As new ventures seek to commercialize nanotechnology, they evolve value creation strategies to better link fundamental scientific advance with the creation of value for users and investors. This paper asks “How do the successful value creation strategies of technology ventures differ in process vs. product-based innovation?” An investigation of 12 ventures representing the extremes of value creation through process-based (nanotech) and product-based (fuel cell) innovation reveals significant differences in their value creation challenges, in the mechanisms of technology–market matching and alliance building, and in their levels of experimentation. Ventures exploiting process innovation faced greater uncertainty in their value chain positioning, market breadth, customization, and the changes required of their customers in contrast to product-based ventures. Our evidence shows that nanotechnology ventures benefit from prioritizing technology–market matching, alliance building and experimenting with technologies in new value networks.