Adolescence is a significant period for the formation of relationship networks and the development of internalizing problems. With a sample of Chinese adolescents (N = 3,834, 52.01% girls, Mage = 16.68 at Wave 1), the present study aimed to identify the configuration of adolescents’ relationship qualities from four important domains (i.e., relationship quality with mother, father, peers, and teachers) and how distinct profiles were associated with the development of internalizing problems (indicated by depressive and anxiety symptoms) across high school years. Latent profile analysis identified a five-profile configuration with four convergent profiles (i.e., relationship qualities with others were generally good or bad) and one “Father estrangement” profile (i.e., the relationship quality with others were relatively good but that with father was particularly poor). Further conditional latent growth curve analysis indicated the “Father estrangement” profile was especially vulnerable to an increase in the internalizing problems as compared with other relationship profiles. This study contributes to understanding the characteristics of interpersonal relationship qualities and their influences on adolescent internalizing problems in a non-Western context. Results were further discussed from a culturally specific perspective.