Objective Addict's spouses are exposed to many psychological problems due to the consequent difficulties they experience in their lives. Therefore, they need training for dealing with these circumstances. Thus, the aim of this study was to investigate the effectiveness of acceptance and commitment therapy in psychological flexibility and psychological capital among methadone-treated individuals' spouses. Method A quasi-experimental research design along with pre-test, post-test, follow-up, and control group was employed for the conduct of the present study. The statistical population of this study included all spouses of methadone-treated patients in addiction treatment clinics in Semnan. From among this population, 30 spouses were selected by random sampling and were randomly assigned to experimental and control groups. In the pre-test stage, both groups responded to Connor-Davidson Resilience Scale, Snyder's Hope Scale, Sherer Self-efficacy Scale, Optimism Scale, and Psychological Flexibility Scale. The experimental group received eight sessions of acceptance and commitment therapy; then, the participants took a post-test and a 2-month follow-up. Results The results of covariance analysis indicated the effectiveness of acceptance and commitment therapy in psychological flexibility and psychological capital (hope, optimism, resilience, and self-efficacy) in the experimental group in both post-test and follow up phases (p <0. 05). Conclusion The findings show that acceptance and commitment therapy can improve the psychological capabilities of addicts' spouses and this treatment can be used along with other treatments.