Children show marked improvements in executive functioning (EF) between 4 and 7 years of age. In many societies, this time period coincides with the start of formal school education, in which children are required to follow rules in a structured environment, drawing heavily on EF processes such as inhibitory control. This study aimed to investigate the longitudinal development of two aspects of inhibitory control, namely response inhibition and response monitoring and their neural correlates. Specifically, we examined how their longitudinal development may differ by schooling experience, and their potential significance in predicting academic outcomes. Longitudinal data was collected in two groups of children at their homes. At T1, all children were roughly 4.5 years of age and neither group had attended formal schooling. One year later at T2, one group (P1, 40 children) had completed one full year of schooling while the other group (KG, 40 children) had stayed in kindergarten. Behavioural and brain activation data (measured with functional near-infrared spectroscopy, fNIRS) in response to a Go/No-Go task and measures of academic achievement were collected. We found that P1 children, compared to KG children, showed a greater change over time in activation related to response monitoring in the bilateral frontal cortex. The change in left frontal activation difference showed a small positive association with mathematical ability, suggesting certain functional relevance of response monitoring for academic performance. Overall, the school environment is important in shaping the development of the neural network underlying performance monitoring.