The aim of this study was to identify clinical risk factors for unfavorable pain trajectories after breast cancer surgery, to better understand the association between pain expectation, psychological distress, and acute postoperative pain. This prospective study included 563 women treated for breast cancer. Psychological data included questionnaires for depressive symptoms and anxiety. Experimental pain tests for heat and cold were performed before surgery. The amount of oxycodone needed for satisfactory pain relief after surgery was recorded. Pain intensity in the area of operation before surgery and during the first postoperative week and expected intensity of postoperative pain were recorded using the Numerical Rating Scale (NRS 0-10). Pain trajectories were formed to describe both initial intensity (the intercept) and the direction of the pain path (the slope). Factors associated with higher initial pain intensity (the intercept) were the amount of oxycodone needed for adequate analgesia, psychological distress, type of axillary surgery, preoperative pain in the area of the operation, and expectation of postoperative pain. The higher the pain initially was, the faster it resolved over the week. Expectation of severe postoperative pain was associated with higher scores of both experimental and clinical pain intensity and psychological factors. The results confirm that acute pain after breast cancer surgery is a multidimensional phenomenon. Psychological distress, pain expectation, and the patients' report of preoperative pain in the area to be operated should be recognized before surgery. Patients having axillary clearance need more efficient analgesic approaches.