This study aimed to examine the mediating role of self-esteem in the relationship between emotional intelligence and psychological adjustment among university students. The study was conducted on a sample of 204 students from the University of Oran 2 - Mohammed Ben Ahmed, comprising 127 females and 77 males, with a mean age of 20.37 years (SD = 1.92). Three scales were administered: the Brief Psychological adjustment Scale developed by Cruz et al. (2019), the Wong and Law Emotional Intelligence Scale (2002), and the Rosenberg Self-Esteem Scale (1965). Mediation analysis was used to examine the relationships among the variables. The results showed a positive correlation between emotional intelligence and self-esteem (r = 0.347, p < .01), as well as between self-esteem and psychological adjustment (r = 0.303, p < .01), whereas no significant direct correlation was found between emotional intelligence and psychological adjustment (r = 0.076). The mediation analysis showed that emotional intelligence significantly predicted self-esteem (β = 0.18, p < .001), and that self-esteem significantly predicted psychological adjustment (β = 0.45, p < .001). The direct effect of emotional intelligence on psychological adjustment was not statistically significant (β = −0.02, p = .606), whereas the indirect effect through self-esteem was statistically significant (β = 0.08, 95% CI [0.04, 0.14]).