The aim of this cross-sectional study is to investigate the role of psychological inflexibility in the relationship between anxiety and depression and emotional eating in a sample of 123 inpatient Italian adult individuals with obesity. Participants completed the Anxiety and Depression subscales of the Psychological General Well-Being Inventory, the Acceptance and Action Questionnaire, and the Emotional Eating subscale of the Dutch Eating Behavior Questionnaire to assess anxiety and depression, psychological inflexibility, and emotional eating, respectively. Results showed that the indirect effect of PGWBI-A on DEBQ-EE through AAQ-II was significant [b = −0.0155; SE = 0.076; 95% BC-CI (−0.0320 to −0.023)]. Similarly, the indirect effect of PGWBI-D on DEBQ-EE through AAQ-II was significant [b = −0.0383; SE = 0.0207; 95% BC-CI (−0.0810 to −0.0002)]. These findings may help to plan and develop specific psychological interventions aimed at addressing emotional eating through targeting psychological inflexibility to be included in obesity treatment programs.