In the last decade, advances in neuroimaging technologies have given rise to a large number of research studies that investigate the neural underpinnings of executive function (EF). EF has long been associated with the prefrontal cortex (PFC) and involves both a unified, general element, as well as the distinct, separable elements of working memory, inhibitory control and set shifting. We will highlight the value of utilising advances in neuroimaging techniques to uncover answers to some of the most pressing questions in the field of early EF development. First, this review will explore the development and neural substrates of each element of EF. Second, the structural, anatomical and biochemical changes that occur in the PFC during infancy and throughout childhood will be examined, in order to address the importance of these changes for the development of EF. Third, the importance of connectivity between regions of the PFC and other brain areas in EF development is reviewed. Finally, throughout this review more recent developments in neuroimaging techniques will be addressed, alongside the implications for further elucidating the neural substrates of early EF development in the future.