Self-compassion, which directs the awareness of suffering, sympathetic concerns and caring motives towards oneself, is an important psychological quality and resource for health and well-being. In the context of physical activity, self-compassion can help individuals overcome obstacles, recuperate from a setback or a lapse and engage in regular physical activity. The present research was the first to examine the longitudinal effects of self-compassion on physical activity and the mediation role of barrier self-efficacy of such effects. We recruited a national representative sample of 654 UK adults and followed them over three timepoints across 9 months. At each time point, participants completed an online survey assessing levels of state self-compassion, barrier self-efficacy and physical activity behaviours. We examined the longitudinal effects of self-compassion on physical activity and the mediation role of barrier self-efficacy. Baseline state self-compassion consistently correlated with physical activity levels at Times 2 and 3. Barrier self-efficacy at Time 2 mediated the longitudinal effect of baseline state self-compassion on Time 3 physical activity, after controlling for within- (e.g., Time 1 on Time 2 self-compassion) and between-person variations (e.g., covariance of self-compassion and physical activity within a timepoint). Adopting a self-compassionate mind facilitates engagement and maintenance of physical activity. Future studies could consider accelerometer-based physical activity measures and develop and validate a more context-specific state self-compassion measure tailored for physical activity contexts. Researchers and practitioners should consider incorporating self-compassion to future interventions and education programmes for promoting physical activity.