Children differ from adults in their physiology and cognitive ability. Thus, they are extremely vulnerable to classroom thermal comfort. However, very few reviews on the thermal comfort of primary school students are available. Further, children-focused surveys have not reviewed the state-of-the-art in thermal comfort prediction using machine learning (AI/ML). Consequently, there is a need for discussion on children-specific challenges in AI/ML-based prediction. This article bridges these research gaps. It presents a comprehensive review of thermal comfort studies in primary school classrooms since 1962. It considers both conventional (non-ML) studies and the recent AI/ML studies performed for children, classrooms, and primary students. It also underscores the importance of AI/ML prediction by analyzing adaptive opportunities for children/students in classrooms. Thereafter, a review of AI/ML-based prediction studies is presented. Through an AI/ML case-study, it demonstrates that model performance for children and adults differs markedly. Performance of classification models trained on ASHRAE-II database and a recent primary students’ dataset shows a 29% difference in thermal sensation and 86% difference in thermal preference, between adults and children. It then highlights three major children-specific AI/ML challenges, viz., “illogical votes”, “multiple comfort metrics”, and “extreme class imbalance”. Finally, it offers several technical solutions and discusses open problems.