This study tested a moderated mediation model that included critical thinking disposition (independent variable), emotional intelligence (moderator), academic self-efficacy (mediator), and academic achievement (dependent variable) in a sample of 642 high school participants aged 14-16 years (M = 15.59, SD = 0.97, 48.44% males) in China, using data from an in-school questionnaire. Study findings showed that critical thinking disposition was positively associated with academic achievement. Academic self-efficacy played a mediating role between critical thinking disposition and academic achievement. Moreover, emotional intelligence played a moderating role in the second half of the mediation process, in which critical thinking disposition affected academic achievement through academic self-efficacy. The results revealed the mechanism of critical thinking disposition on academic achievement.