Introduction Leadership, and the role of a Chief Executive in healthcare organisations, has never been more important. This review provides one of the first retrospective cross-sectional analyses of the developmental journeys of chief executives within the National Health Service (NHS).

Methods Twenty-eight semi-structured qualitative interviews were conducted with medical, clinical and non-clinical NHS chief executives from the Health Service Journal’s list of ‘Top Chief Executives’ 2014–2018. Through a thematic analysis of their narratives, lessons for the development of aspiring NHS chief executives emerge.

Results Few proactively sought leadership opportunities and there was a lack of an active leadership development strategy. Yet the ‘seeds of leadership development’ took root early. Combined with a blended approach of formal leadership development and ‘on-the-job’ informal leadership development, emerging NHS chief executives were exposed to multiple ‘crucible moments’ that helped them develop into and excel at the top of their field.

Discussion Top NHS chief executives possess inherent values and a strong sense of social responsibility that underpin their developmental journeys, guide their behaviour, and strengthen their resilience. Capable, high quality leaders are needed from all professional backgrounds to support high quality care and much more needs to be done, particularly for medical and clinical professionals but for non-clinicians too, to maximise leadership potential within the NHS and develop a pipeline of aspiring NHS chief executives.