To explore the profiles of psychological flexibility among dementia family caregivers and examine their associations with psychological well-being and caregiving factors. Participants were 521 dementia family caregivers in Japan. Latent profile analysis was conducted to explore the profiles of psychological flexibility. The analyses examined differences in depression, anxiety, life satisfaction, and work-family conflict/enrichment between the profiles, and whether sociodemographic variables and caregiving stressors predict the profile. Four distinct profiles were identified: high psychological flexibility (14.2%), moderate psychological flexibility with high commitment (24.7%), moderate psychological flexibility with low commitment (48.0%), and low psychological flexibility (13.1%). The low psychological flexibility profile exhibited the highest scores of depression, anxiety and work-family conflict, followed by the moderate psychological flexibility with low/high commitment profiles, and the high psychological flexibility profile. The high psychological flexibility and moderate psychological flexibility with high commitment profiles exhibited higher life satisfaction than the moderate psychological flexibility with low commitment profile. Caregiving stressors, marital status, and caregiver status predicted the profile. Enhancing defusion and acceptance, rather than increasing commitment to personal values, may be beneficial in supporting distressed caregivers. Having more caregiving stressors, being single/divorced/bereaved, and being a primary caregiver may be useful indicators of decreased psychological flexibility among dementia family caregivers.