During the COVID-19 pandemic, online teaching modes were found vital to continue students’ learning process, but sustainable implementation of online teaching models is an area of concern for policymakers. Psychiatrists are also eager to know students’ behavior toward learning and modes of teaching during COVID-19. We have drawn a model based on the big five personality traits to study students’ satisfaction with online teaching modes and their adoption intentions toward online teaching modes. We have collected data from 718 bachelor’s and master’s level students from four different universities. We have applied the SEM-ANN dual-stage approach to test personality traits’ influence and ranked them based on their normalized importance. The results revealed that agreeableness, conscientiousness, neuroticism, and openness positively influence students’ satisfaction with online teaching models, but that extraversion negatively influences their satisfaction. Agreeableness, extraversion, and neuroticism positively impact, but openness negatively influences. Conscientiousness does not affect adoption intention. Furthermore, agreeableness is the most significant, and conscientiousness is the least important factor for students to adopt online teaching modes. The findings of the study have useful perceptiveness for educational policymakers, academics, and psychiatrists.