Previous studies documented gender-related differences in the expression of Perinatal Affective Disorders. However, little attention has been paid to screening the male population during the perinatal period. This study was based on three aims: (1) to investigate the mental health of expectant fathers based on their levels of depression, anxiety, addiction, anger attacks/hostility, and somatization, identifying psychological profiles; (2) to analyze the association between these profiles and the individual variable of perceived stress; (3) and to examine the association between these profiles and the couple’s variable of marital adjustment. A total of 350 Italian expectant fathers in the last trimester of pregnancy were asked to fill in questionnaires concerning perceived stress, dyadic adjustment, psychiatric symptomatology, and depression. Three different clusters were found: “psychologically healthy men” (68%) with low levels of symptoms on all the scales; “men at risk of externalized behavioral problems” (17.1%), characterized by one or more addictive or risky behaviors and moderate levels of scales scores; and “men experiencing psychological distress” (14.9%), with the highest scores on all the scales. A significant association emerged among the perceived stress, marital adjustment, and cluster membership. These results highlight the importance of screening fathers in perinatal health services, which are still predominantly mother-centered, and underscore the necessity to create tailored and personalized interventions.