Developmental executive function (EF) theories have proposed distinct domains of EF (cool and hot) but the EF development in autism spectrum disorder (ASD) has been assessed mainly with cool EF measures. Little is known regarding the development of hot EF in ASD. EF is suggested to strongly associate to theory of mind (ToM) in typical development but the correlation between hot EF and ToM is understudied in ASD. The current study was aimed at investigating the cross-sectional developmental changes of cool and hot EF in middle childhood and adolescence and their association to ToM in ASD. Eighty-two children and adolescents (7–16 years) were assessed with measures of cool EF (inhibition, working memory, planning, and cognitive flexibility), hot EF (affective decision-making and delay discounting), and ToM (2nd-order false belief and ignorance; mental state/emotion recognition). Our results showed that the trajectories of all cool EF presented linear age-related improvements in ASD. In terms of hot EF, trajectories demonstrated non-linear functions of age for affective decision-making and delay discounting. Both EF domains were found to associate with ToM over and above age, while hot EF associated with ToM over and above cool EF as well. The investigation of the developmental trajectories of cool and hot EF may help define potential cognitive phenotypes across age within ASD.