This paper discusses the experience of UK doctoral graduates in pursuing entrepreneurial careers: there is evidence that this applies to a substantial number – about 10% – of doctoral graduates. The nature of their experience was explored using 37 interviews with doctoral entrepreneurs. The research was funded by Vitae ( www.vitae.ac.uk ), an organization championing the personal, professional and career development of doctoral researchers and research staff in UK higher education. The stories that the participants tell suggest that doctoral entrepreneurship develops out of a complex interaction between the personality and skills of the entrepreneurs and the environment in which they operate. In particular, the authors argue that the participants have mobilized a mix of financial, social and educational capital in order to create and sustain their enterprises successfully.