This study used latent profile analysis to analyze the subgroups of psychological flexibility (PF) profiles based on key subcomponents of PF in college students, and how the subgroups were related to college adjustment and subjective well-being. A sample of 644 participants from a Chinese vocational college completed the questionnaires online. We found three distinct profiles of PF: high psychological flexibility (HPF), moderate psychological flexibility (MPF), and low psychological flexibility (LPF). College adjustment and subjective well-being were significantly different across the three PF profiles, with HPF individuals adjusting the best to college life and having the highest well-being, whereas LPF individuals adjusted the worst to college life and had the lowest wellbeing. Moreover, students from rural areas and students with siblings were characterized by LPF. The results of this study provide a new vision for understanding PF in college students using a person-oriented approach.