Parenting sense of competence refers to parents’ perception about their ability to perform the parenting role, one of the key dimensions in family dynamics. This construct is even more important in families at psychosocial risk, where the exercise of parenting can be more challenging. The Parenting Sense of Competence scale (PSOC) is a self-report measure that aims to assesses one’s perceived efficacy and satisfaction with parenting. In this cross-sectional and instrumental study, we aimed to examine the psychometric properties of the PSOC among a Portuguese sample of community (n = 205) and at-psychological-risk (n = 273) parents. Participants completed the PSOC, the Enrich Marital Satisfaction Scale, the Parenting Stress Index, and the Parenting Alliance Inventory. Results from confirmatory factor analysis showed that a two-factor revised model obtained the best fit, with some items being removed. Our data confirmed that the PSOC has good psychometric properties, with acceptable reliability and validity and measurement invariance across the community and the at-risk samples. Findings of this psychometric exploration provided evidence that the PSOC is a reliable measure of easy application and interpretation for assessing the perceived competence of Portuguese parents.