Substance use has long been associated with close relationship distress. Although the direction of influence for this association has not been established, it has often been assumed that substance use is the causal agent and that close relationship distress is the effect. But research seeking to establish temporal precedence in this link has produced mixed findings. Further, theoretical models of substance use and close relationship processes present the plausibility of the inverse pathway—that insecure close relationships may serve as a vulnerability factor for the development of later substance problems. The current review applies an attachment-theoretical framework to the association between close social bonds and substance use and substance-related problems. Targeting longitudinal studies of attachment and substance use, we examined 665 effect sizes drawn from 34 samples (total N = 56,721) spanning time frames ranging from 1 month to 20 years (M = 3.8 years). Results revealed a significant prospective correlation between earlier attachment and later substance use (r = −.11, 95% CI [−.14, −0.08]). Further, cross-lagged coefficients were calculated which parsed auto-regressive effects, indicating that lower attachment security temporally preceded increases in substance use (r = −.05, 95% CI [−.06, −.04]). Analyses further indicated that the pathway from earlier attachment to later substance use was significantly stronger than that from earlier substance use to later attachment. Results also revealed several moderators of the attachment-substance use link. These findings suggest that insecure attachment may be a vulnerability factor for substance use, and indicate close relationship quality as a promising line of inquiry in research on substance use disorder risk.