ObjectiveThis study examined whether the association between the Big Five personality dimensions and postdivorce adjustment (PDA) was mediated by Neff's concept of self‐compassion.BackgroundResearch on marital psychology suggests that multiple psychological factors are associated with PDA. However, the mechanisms by which these factors affect PDA have received much less attention. Accordingly, in the current study, the potential mediation effect of self‐compassion was investigated. Cultural context of PDA is considered.MethodA total of 334 divorced Iranian women took part in the study. Participants completed a sociodemographic survey, including the Ten‐Item Personality Inventory (TIPI), the Self‐Compassion Scale–Short Form (SCS‐SF), and Fisher's Divorce Adjustment Scale (FDAS).ResultsCorrelational analyses and structural equation modeling showed a significant positive association of self‐compassion with self‐reported measures of the positive factors of PDA (feeling of self‐worth, disentanglement from love relationships, social self‐worth, and rebuilding social trust), and the personality traits of emotional stability, extraversion, and conscientiousness. There also was a significant negative association with the negative factors of PDA (symptoms of grief and feeling of self‐anger) and the personality traits of agreeableness, and openness to experience. Self‐compassion significantly predicted variation in positive psychological health beyond that attributable to personality; it partially mediated the relationship between personality and postdivorce adjustment.ConclusionsPersonality appears to relate to postdivorce adjustment through self‐compassion. The role of Iranian cultural characteristics in perceiving the magnitude of stress resulting from divorce, and postdivorce adjustment is discussed.ImplicationsEnhancing self‐compassion among divorced Iranian women seems to be a worthwhile approach to divorce counseling.