Cardiac rehabilitation (CR) participation after percutaneous coronary intervention (PCI) for coronary heart disease lowers the disease burden and risk of recurrent cardiac events. Examining psychological factors may improve post-PCI health behavior adherence. To determine whether psychological factors are associated with post-PCI health behavior adherence, and the role of CR participation. Data from 1,682 patients (22.1% female, Mage = 64.0, SDage = 10.5 years) from the THORESCI cohort were included. Adjusted mixed models were used to examine associations between psychological factors and the 1-year course of health behaviors, using interactions to test for moderation by CR participation. Psychological factors were associated with the trajectories of adherence to medical advice, exercise, and diet. The strongest association found was between optimism and the trajectory of dietary adherence (B: = -0.09, p = .026). Patients with high optimism levels had a worse trajectory of dietary adherence compared to patients with low to middle optimism levels. Participation in CR buffered the associations of high anxiety, pessimism, and low to middle resilience, but strengthened the associations of high stress in the past year with the probability of smoking. Psychological factors are associated with post-PCI health behavior adherence, but the pattern of associations is complex. Patients with high levels of anxiety, pessimism, and low to middle resilience levels may disproportionately benefit from CR. Cardiac rehabilitation programs could consider this to improve post-PCI health behavior adherence. NCT02621216.