Family functioning is salient in explaining adolescents’ problematic internet use (PIU), and precisely this family functioning is under pressure after parental divorce. Moreover, growing up with divorced parents is identified as a risk factor for PIU. Therefore, examining which factors are associated with adolescents’ PIU after divorce is particularly important. Based on self-report data from N = 244 adolescents of divorced families (49.6% boys, M = 13.42), structural equation modeling (SEM) was used to examine the associations of PIU with interparental conflict, triangulation, maternal and paternal warmth, and adolescents’ self-esteem. Potential buffering effects of self-esteem were tested, as well as gender differences in associations. The results showed that more triangulation and less maternal warmth were related to higher levels of PIU, but these effects disappeared after adding self-esteem to the models. Adolescent self-esteem did not significantly buffer the effects of the different family factors on PIU, nor were there any significant gender differences in association. Hence, especially adolescents’ self-esteem seems to be a key aspect for PIU in adolescents from divorced families.