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Problem behaviors among rural adolescents remain a significant public health concern, yet the temporal roles of key psychosocial resources are not well understood. Grounded in Conservation of Resources theory and Problem Behavior Theory, this study examined the longitudinal associations between psychological capital, perceived social support, and problem behaviors among rural Chinese adolescents. A three-wave, one-year longitudinal design was conducted with 770 adolescents (49.86% male, Mage = 16.36, SD = 1.57). Random-intercept cross-lagged panel models were applied to disentangle stable between-person differences from within-person processes. At the between-person level, adolescents with higher overall psychological capital and perceived social support reported lower levels of problem behavior. At the within-person level, psychological capital showed a time-specific protective effect, with short-term increases predicting subsequent reductions in problem behavior, whereas problem behavior did not predict later psychological capital. In contrast, perceived social support demonstrated reciprocal associations with problem behavior: higher support predicted later decreases in problem behavior, while elevated problem behavior predicted subsequent declines in perceived support. These findings indicate that psychological capital and perceived social support operate through distinct temporal mechanisms and highlight the importance of early internal resource development and sustained relational support in rural adolescent populations.