The Sexual Excitation Sexual/Inhibition Inventory for Women and Men (SESII-W/M) and the Sexual Excitation Scales/Sexual Inhibition Scales short form (SIS/SES-SF) are two self-report questionnaires for assessing sexual excitation (SE) and sexual inhibition (SI). According to the dual control model of sexual response, SE and SI differ between individuals and influence the occurrence of sexual arousal in given situations. Extreme levels of SE and SI are postulated to be associated with sexual difficulties or risky sexual behaviors. The present study was designed to assess the psychometric properties of the German versions of both questionnaires utilizing a large population-based sample of 2,708 participants (Mage = 51.19, SD = 14.03). Overall, psychometric evaluation of the two instruments yielded good convergent and discriminant validity and mediocre to good internal consistency. The original 30-item version of the SESII-W/M did not show a sufficient model fit. For a 24-item version of the SESII-W/M partial strong measurement invariance across gender, and strong measurement invariance across relationship status, age, and educational levels were established. The original structure (14 items, 3 factors) of the SIS/SES-SF was not replicated. However, a 4-factor model including 13 items showed a good model fit and strong measurement invariance across the before-mentioned participant groups. For both questionnaires, partial strong measurement invariance with the original American versions of the scales was found. As some factors showed unsatisfactory internal consistency and the factor structure of the original scales could not be replicated, scores on several SE- and SI-factors should be interpreted with caution. However, most analyses indicated sufficient psychometric quality of the German SESII-W/M and SIS/SES-SF and their use can be recommended in German-speaking samples. More research with diverse samples (i.e., different sexual orientations, individuals with sexual difficulties) is needed to ensure the replicability of the factor solutions presented in this study.