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The current literature highlights the significant role of psychological factors including cognitive (pain related thoughts and beliefs) and acceptance components (pain willingness, activity engagement, psychological inflexibility) in the management of chronic pain. The research is however in the preliminary stages in terms of investigating the specific relationships that exist between these psychological processes in their ability to predict adjustment to pain. This study aims to extend the current findings by investigating the relationships between several cognitive and acceptance components in their ability to predict emotional and physical adjustment in the context of chronic pain. The hypotheses that cognitive and acceptance components mediate the relationship between pain severity and pain adjustment, and also that acceptance mediates the relationship between cognitive components and pain adjustment will be tested. Method The study employed a cross-sectional survey-based design, including 214 chronic pain patients recruited from an NHS pain clinic. Participants completed a series of self-report questionnaires measuring pain severity, fear of movement beliefs, pain self-efficacy beliefs, pain catstrophising, acceptance and psychological flexibility, pain disability, and depression and anxiety. Structural Equation Modeling was used in order to conduct path analyses, investigating the complex relationships between these variables in predicting physical and emotional adjustment to chronic pain. Results The results from a Confirmatory Factor Analysis indicated that a three factor model comprising pain, cognitive and acceptance components as separate latent variables had a poor fit and therefore could not be used in further analysis. The results of path analyses showed that pain self-efficacy was the only variable to have a strong mediating influence between pain and physical adjustment. Findings also supported a nested path model demonstrating that acceptance, catastrophising and self-efficacy were mediators between pain and emotional adjustment, and that acceptance was also a mediator for pain catastrophising and a partial mediator for pain self-efficacy in their relationship with emotional adjustment. Conclusions The importance of pain self-efficacy specifically in predicting physical adjustment to pain is highlighted. A more complex model however is required to explain emotional adjustment, with acceptance playing a more prominent role in comparison with other variables. The findings also provide support for both Cognitive and Acceptance-based interventions in improving adjustment to living with chronic pain. Given the preliminary nature of these findings, further research employing similar statistical methods are required to provide further support.