The five Cs model of positive youth development describes adolescents' development as reflecting five distinct but related domains of Competence, Confidence, Character, Connection, and Caring. This research used confirmatory factor analysis (CFA) and exploratory structural equation modeling (ESEM) to test the five Cs model in a Chinese sample of 384 adolescents (49.6% males; mean of age = 15.13 years old). The results showed that ESEM had better fit and relatively smaller factor correlations than CFA. In addition, factors such as Connection and Caring were well defined by their target indicators, although several non-target indicators significantly loaded onto Confidence factor in ESEM analysis. These results suggest that the correlations between some factors might be greatly overestimated in previous research based on CFA. The implication that ESEM is a more appropriate approach for testing the factor structure of the five Cs model of PYD is discussed.