The quality of educational environments and sustainable architectural features are considered important factors in improving the learning process, enhancing mental concentration, and promoting academic performance. Among these factors, thermal comfort, as one of the most important dimensions of indoor environmental quality, plays a significant role in enhancing the productivity of occupants in educational spaces. This study aims to conduct a multivariate analysis of the effects of thermal comfort and sustainable architectural features on students’ learning quality and academic performance in educational environments. In terms of purpose, the study is applied, while its methodological approach is descriptive-correlational. The statistical population consisted of students enrolled at universities in Ilam, Iran, from whom 220 participants were selected using systematic random sampling. Data were collected in actual classroom settings during educational activities in summer, autumn, and winter. Students’ perceptions of and satisfaction with thermal conditions were assessed using a questionnaire. Thermal environmental parameters, including air temperature, relative humidity, air velocity, mean radiant temperature, metabolic rate, and clothing insulation, were measured using a Delta OHM HD32.1 instrument. Cognitive performance was also assessed using standardized tests. The data were analyzed using SPSS version 22, Pearson’s correlation coefficient, and multiple regression analysis, with the significance level set at 0.05. The results indicated statistically significant relationships among the examined variables (p < 0.001). Thermal comfort exhibited the strongest reported effect (β = 0.62, t = 6.84), followed by mental concentration (β = 0.55), academic performance (β = 0.51), learning satisfaction (β = 0.47), environmental productivity (β = 0.43), and architectural sustainability (β = 0.39). The findings suggest that improving thermal comfort and incorporating sustainable architectural principles may be associated with enhanced concentration, greater learning satisfaction, and improved academic performance. These results highlight the importance of integrating thermal comfort considerations and sustainable design strategies into educational environments to support students’ learning experiences and academic outcomes.