A long line of research in Positive Psychology highlights Psychological Capital (PsyCap) as a key factor in forecasting post-secondary students' academic adjustment. Such work, however, focuses on the adaptation of typical students. Studies with a focus on exceptional students, such as those with learning difficulties, pinpoint their marked disadvantages but have not considered PsyCap as a positive construct in their academic adjustment. This study compared the PsyCap and academic adjustment of 251 students with learning disabilities (LD, 40 males and 83 females, mean age 26), or attention deficit hyperactivity disorder (ADHD, 31 males and 97 females, mean age 27) to 250 typical counterparts (83 males and 167 females, mean age 25). It was designed to clarify whether PsyCap mediated the relationship between participant group and academic adjustment. Findings suggested LD/ADHD students manifest lower levels of PsyCap and academic adjustment. PsyCap was a significant mediator in the relationship between participant group and academic adjustment. Findings also pointed to a strong, positive relationship between PsyCap and academic adjustment, with a uniform magnitude for the two groups. The importance of the findings are discussed with direct reference to PysCap's role in post-secondary academic adjustment.