Improved understanding of psychological features associated with full mu agonist long-term opioid therapy (LTOT) cessation may offer advantages for clinicians. This preliminary study presents changes in psychological outcomes in patients with chronic, non-cancer pain (CNCP) after LTOT cessation via a 10-week multidisciplinary program which included treatment with buprenorphine. Paired t-tests pre- and post-LTOT cessation were compared in this retrospective cohort review of data from electronic medical records of 98 patients who successfully ceased LTOT between the dates of October 2017 to December 2019. Indicators of quality of life, depression, catastrophizing, and fear avoidance, as measured by the 36-Item Short Form Survey, the Patient Health Questionnaire-9-Item Scale, the Pain Catastrophizing Scale, and the Fear Avoidance Belief Questionnaires revealed significant improvement. Scores did not significantly improve for daytime sleepiness, generalized anxiety, and kinesiophobia, as measured by the Epworth Sleepiness Scale, the Generalized Anxiety Disorder 7-Item Scale, and the Tampa Scale of Kinesiophobia. The results suggest that successful LTOT cessation may be interconnected with improvements in specific psychological states.