(1) Background: This study evaluated the psychometric properties of the Condom Use Self-Efficacy Scale among Colombian youth. (2) Method: A total of 2873 men and women between 18 and 26 years old (M = 21.45, SD = 2.26) took part in this study. All participants answered a socio-demographic survey, the Condom Use Self-Efficacy Scale, the UCLA Multidimensional Condom Attitudes Scale, The Condom Use Errors and Problems Scale, and the Sexual Assertiveness Scale. Sampling was web-based, and the survey was distributed via Facebook. (3) Results: The Condom Use Self-Efficacy Scale demonstrated adequate reliability (ordinal α ranged = 0.76 to 0.92). Exploratory and confirmatory factor analysis suggested a four-factor structure with an explained variance of 69%. This dimensionality was also invariant across gender. Moreover, positive attitudes toward condom use were significantly associated with appropriation and assertiveness. Two dimensions (appropriation and partner disapproval) showed significant gender differences. (4) Conclusions: The Spanish–Colombian version of the Condom Use Self-Efficacy Scale is a psychometrically adequate instrument to measure perceived condom use self-efficacy. This scale can be used in both research and professional settings to measure self-efficacy at using condoms in young people.