A large body of literature has established that children orphaned by HIV/AIDS (‘AIDS orphans’) face numerous challenges, such as parental death, poverty, disrupted school attendance and stigma. All of these early life adversities can have long-lasting effects on brain function, especially the executive functions. Working memory, as one of the most studied aspects of executive functions, is also reported to be impaired in children with early adversity. However, limited data are available regarding how early life adverse events affect the neural dynamic associated with working memory processing in AIDS orphans. This study applied the electroencephalogram (EEG) technique to investigate the working memory process in 81 AIDS orphans and 62 non-orphan controls with n-back tasks. Results from EEG analysis and time-frequency analysis showed that AIDS orphans displayed smaller N2 and larger P2, P3 activation as well as enhanced theta and attenuated alpha band oscillations compared to the controls. The present findings indicated a deficit in working memory process in AIDS orphans and suggested that this deficit might be due to the impairments in attention allocation, detection and classification of stimuli and updating process in working memory.