Objectives To investigate the experiences of doctors who become chief executives of NHS organizations, with the aim of understanding their career paths and the facilitators and barriers encountered along the way. Design Twenty-two medical chief executives were identified and of these 20 were interviewed. In addition two former medical chief executives were interviewed. Information was collected about the age at which they became chief executives, the number of chief executive posts held, the training they received, and the opportunities, challenges and risks they experienced. Setting All NHS organizations in the United Kingdom in 2009. Results The age of medical chief executives on first appointment ranged from 36 to 64 years, the average being 48 years. The majority of those interviewed were either in their first chief executive post or had stepped down having held only one such post. The training and development accessed en route to becoming chief executives was highly variable. Interviewees were positive about the opportunity to bring about organizational and service improvement on a bigger scale than is possible in clinical work. At the same time, they emphasized the insecurities associated with being a chief executive. Doctors who become chief executives experience a change in their professional identity and the role of leaders occupying hybrid positions is not well recognized. Conclusions Doctors who become chief executives are self-styled 'keen amateurs' and there is a need to provide more structured support to enable them to become skilled professionals. The new faculty of medical leadership and management could have an important role in this process.