Phantom Limb Pain (PLP) is a phenomenon commonly observed in orthopedic rehabilitation units that can have detrimental effects on patients’ functioning. Psychological aspects of PLP have been widely investigated showing that some coping mechanisms are advantageous at certain points but not at others. However, the mechanisms related to positive adjustment to PLP during the course of rehabilitation have not been adequately examined. The aim of the study was to investigate the relationship between PLP and coping mechanism at two points during the rehabilitation process. Thirty one orthopedic inpatients, who had undergone lower-limb amputation following diabetic complications, rated their pain levels and mental coping strategies. The Ways of Coping Checklist, Life Orientation Test, and the McGill Pain Questionnaire, 1-15 days post-surgery and six months post-surgery were used for evaluation. Denial was found to be negatively correlated with PLP shortly after amputation. In contrast, optimism was found to be negatively correlated with PLP six months after the surgery. Emotion-focused coping mechanisms were found to be positively correlated with PLP. It is concluded that denial during the early stages of recuperation and optimism at later stages of rehabilitation is associated with reduced PLP. Awareness of these mental processes by both medical staff and family members may enable acceptance of these processes and thus facilitate patients’ rehabilitation.