This study aimed to examine the role of decentering and committed action as mediators of the link of external and internal shame with psychological health, in people with a chronic disease diagnosis (n = 223) and without chronic disease (n = 230). Participants with chronic disease presented higher levels of both external and internal shame. Path analysis results showed that these variables seem to be negatively linked to psychological health and that their effects on this outcome seem to be reduced by the mechanisms of decentering and committed action. The tested model explained 56% of psychological health's variance and was invariant across groups. This study emphasizes the importance of taking a decentered stance towards internal experiences and behaving accordingly to one's personal values on psychosocial functioning, independently of disease status. These results may have particular relevance to individuals with high levels of shame.