Adjustment to the university environment is regarded as an important factor in predicting university outcomes. This study explores the pathways taken by adjustment and other psychosocial variables (help‐seeking, academic motivation, self‐esteem, perceived stress, and perceived academic overload), in relation to the success of economically and educationally disadvantaged students at university. Participants were 194 first‐year students on need‐based financial aid at a South African university; they completed questionnaires that measured these psychosocial variables, and their final first‐year academic results were obtained via the university’s records office. Path analyses showed that adjustment did not function as a pure mediator on academic performance as the dependent variable. Furthermore, the psychosocial factors explained much (59%) of the variance in the students’ adjustment and 20% of the variance in their academic performance. Hence, the psychosocial variables better explained the students’ adjustment to university than academic performance.