Research has consistently demonstrated a relationship between negative childhood experiences and the development of psychological difficulties in adulthood. Yet, it is only recently that the potential mechanisms underlying this relationship have been investigated. An increasing number of studies indicate heightened levels of experiential avoidance as potentially accounting for this relationship. The current review presents research, spanning the last five years, that describes associations and mediating relationships between experiential avoidance, psychopathology and maladaptive behaviours. However, whilst recent advances in the measurement of experiential avoidance, and newly emerging research, have broadened psychological understanding of this construct, conceptual and methodological difficulties within this field highlight the need for further research to be undertaken. The empirical paper explores the potential contribution of experiential avoidance, childhood trauma and internalised shame in pathways to becoming and remaining homeless. In a sample of 79 homeless adults, a significant relationship between childhood trauma and experiential avoidance was found which was mediated by internalised shame. These findings indicate that experience of childhood trauma is associated with a greater tendency to avoid unwanted thoughts and feelings, which in turn is associated with greater levels of internalised shame. They further provide support for the role of interacting psychological factors in pathways to homelessness. Clinical implications resulting from this study are discussed, and directions for further research are indicated.