This study aimed to investigate changes in the pain sensory profile of women with breast cancer. Five women with unilateral breast cancer were enrolled. Participants were assessed with direct (quantitative sensory testing, QST) and indirect measures of pain sensitization (self-reported central sensitization inventory, CSI) at baseline (before surgery), 1 week after surgery, and at 1, 6, 9, and 12 months post-surgery. In the event of pain occurrence, the Leeds Assessment of Neuropathic Symptoms and Signs was also used. Nociceptive pain was the predominant pain mechanism in the postoperative period, while an increase in sensitization predominated one year after breast cancer surgery, especially in those participants who had received more treatment procedures. The participants who received more therapies for breast cancer experienced persistent pain and a higher level of sensitization. An assessment protocol including direct measurements (QST) and indirect measurement (self-reported CSI) allows for detecting changes in pain sensitivity, which can be useful for characterizing and/or predicting pain before, during, and up to one year following surgical interventions for breast cancer.