This study’s objective was to examine whether the relationship between actual motor competence and physical activity (PA) in children is mediated by perceived motor competence (PMC) and physical activity enjoyment. The participants consisted of a total of 167 students (male = 92, female = 75) in 10 different schools in the fourth grade of primary schools in the central district of Isparta Province, Turkey, during the 2020–2021 academic year. Multiple parallel mediation analysis was used to examine the mediation role in the analysis of the data, and regression analysis based on the bootstrapping method was performed. As a result of the research, it was seen that PMC had a full mediating role between actual motor competence and PA (b = 0.003, 95% confidence interval [0.002, 0.094]). On the other hand, it was determined that PA enjoyment did not have a mediating role in this relationship (b = 0.001, 95% confidence interval [−0.002, 0.005]). The total indirect effect was not significant (b = 0.005, 95% confidence interval [−0.000, 0.012]). The multiple mediation analysis showed that PMC accounted for 23.2% of the total effect of actual motor competence on PA. In conclusion, the findings show that PMC is an important variable in participation in PA. Therefore, PMC should be considered a key outcome in physical education.