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Background and Aims The complete pathological response (pCR) following neoadjuvant chemotherapy (NAC) in breast cancer is essential for the accurate prediction of prognosis. We aimed to evaluate the efficacy of the presence and type of peritumoral edema detected by magnetic resonance imaging (MRI) in predicting pCR to NAC in breast cancer patients. Methods and Results One hundred five patients with the diagnosis of invasive carcinoma were evaluated by MRI before NAC. Edema was evaluated in fat-suppressed T2-weighted images. The patients were categorized into three groups: patients with no peritumoral edema, patients with peritumoral edema, and patients demonstrating subcutaneous edema. The cases were categorized as being pCR and non-pCR. Molecular subtypes, lymphovascular invasion (LVI), tumor size, and apparent diffusion coefficient (ADC) were evaluated. A positive relationship was found between the presence of edema and tumor size. Subcutaneous edema was found to be statistically higher in non-pCR patients. While the number of pCR patients with subcutaneous edema was 17 (30.4%), the number of non-pCR patients with subcutaneous edema was 26 (53.1%) ( p = 0.018). LVI was found to be statistically higher in patients with edema. The number of edema-negative and LVI (+) patients was 4 (15.4%), while the number of edema-positive and LVI (+) patients was 28 (35.4%) ( p = 0.042). Intratumoral and peritumoral ADC values were significantly higher in tumors with edema. Conclusion The presence of subcutaneous edema and LVI may be utilized for the prediction of pCR outcomes in breast cancer patients scheduled for NAC treatment.