The present study explored heterogeneity in the association between engaged living and problematic Internet use. This study included 641 adolescents from four junior-senior high schools of Guangzhou, China. Besides the standard linear regression analysis, mixture regression analysis was conducted to detect certain subgroups of adolescents, based on their divergent association between engaged living and PIU. Sex, age, and psychological need were further compared among the latent subgroups. The results showed that a mixture regression model could account for more variance of PIU than a traditional linear regression model, and identified three subgroups based on their class-specific regression of PIU to engaged living. For the High-PIU class, lower social integration and higher absorption were associated with increased PIU; for the Medium-PIU class, only high social integration was linked with the increase of PIU. For the Low-PIU class, no relation between engaged living and PIU were found. Additionally, being male or having a lower level of satisfied psychological needs increased the link between engaged living and PIU. The results indicated a heterogeneous relationship between engaged living and PIU among adolescents, and prevention or intervention programs should be tailored specifically to subgroups with moderate or high levels of PIU and to those with lower levels of psychological needs’ satisfaction, as identified by the mixture regression model.