This study examines the relationships between critical thinking, metacognition, psychological well-being, and empathy using structural equation modeling. The study sample consists of 155 university students from a higher education institution in Spain, who completed the PENCRISAL, the metacognitive abilities inventory, the Ryff psychological well-being scale, and the empathy quotient, which assess these psychological constructs. The results indicate that critical thinking has a direct positive effect on metacognition, which, in turn, is significantly associated with higher levels of psychological well-being and empathy. These findings reinforce the essential role of critical thinking in fostering cognitive self-regulation and socioemotional competencies. Furthermore, this study provides empirical evidence supporting the integration of critical thinking into educational programs, emphasizing its potential to enhance reflective thinking, emotional awareness, and interpersonal understanding.