Appearance concerns following burn injuries are common. Psychological factors are important in maintaining such concerns. However, there is a lack of longitudinal or prospective research investigating their development. This study investigated whether psychological flexibility and self-compassion at hospital admission predicted subsequent appearance concerns. A multi-centre prospective cohort study across six burn services. Adults (n = 175; 67% male) in hospital following burn injuries were recruited. Questionnaires measuring appearance concerns, psychological flexibility, self-compassion, post-traumatic stress disorder symptoms and perceived noticeability were completed during hospital admission and two- and six-months later. Demographic and burn injury information was collected. Correlational analyses showed that increased psychological flexibility and self-compassion at admission were associated with decreased appearance concerns cross-sectionally and prospectively at two- and six-month follow-up. These associations remained significant when controlling for key covariates (i.e. gender, age, ethnicity, percentage total body surface area burnt, perceived noticeability, PTSD symptoms). Multiple linear regression analyses revealed that psychological flexibility and self-compassion predicted appearance concerns during hospital admission. Although psychological flexibility significantly predicted appearance concerns over time, it became non-significant when controlling for baseline appearance concerns. Psychological flexibility has a protective role against appearance concerns soon after burn injuries, although this protective role is reduced when accounting for baseline appearance concerns. Early interventions targeting psychological flexibility (i.e. acceptance and commitment therapy) may be beneficial after burns if adapted to address appearance-related concerns.