The aim of this study was to investigate the importance of cognitive structures like Early Maladaptive Schemas and personality traits in men's sexual functioning. 50 men diagnosed with sexual dysfunction from the Sexology Clinic of the Hospitais Universidade de Coimbra, and 50 individuals from the community without sexual dysfunction. Participants answered to the Sexual Dysfunction Inventory (SDI - male version; Sbrocco, Weisberg, & Barlow, 1992), International Index Erectile Function (IIEF; Rosen, Riley, Wagner, Osterloh, Kirkpatrick, & Mishra, 1997), Brief Symptom Inventory (BSI; Derogatis & Spencer, 1982), Beck Depression Inventory (BDI; Beck, Ward, Mendelson, Mock, & Erbaugh, 1961), Young Schemas Questionnaire (YSQ; Young & Brown, 1990), Questionnaire of Cognitive Schema Activation in Sexual Context (QCSASC; Nobre & Pinto-Gouveia, 2006); NEO Five-Factor Inventory (NEO-FFI; Costa & McCrae, 1992). Men with higher sexual functioning show more Openness to Experience (personality dimension) compared to men with lower sexual functioning. Regarding cognitive schemas, men with lower sexual functioning show significantly more Vulnerability schemas and activate with significantly higher frequency Difference/Loneliness, Self-Depreciation, Incompetence and Undesirability/ Rejection schemas when confronted to unsuccessful sexual situations, when compared with men with higher sexual functioning. the findings supported the importance of the cognitive structures, psychopathology and personality variables on sexual functioning.