Objective To explore the accuracy of contrast-enhanced magnetic resonance imaging (MRI) in predicting pathological complete remission (pCR) in breast cancer patients after neoadjuvant therapy (NAC). Methods The clinicopathological data of 245 patients with invasive breast cancer who had completed the surgical resection after NAC in the Affiliated Hospital of Southwest Medical University from March 2020 to April 2022 were collected retrospectively. According to the results of hormone receptor (HR) and human epidermal growth factor receptor 2 (HER2) detected by immunohistochemistry, all patients were divided into four subgroups: HR+/HER2–, HR+/HER2+, HR–/HER2+ and HR–/HER2–. The value of MRI in evaluating the efficacy of NAC was analyzed by comparing the postoperative pathological results as the gold standard with the residual tumor size assessed by preoperative MRI. Meanwhile, the sensitivity, specificity and positive predictive value (PPV) of pCR predicted by the evaluation results of enhanced MRI were analyzed, and further analyzed its predictive value for pCR of different subtypes of breast cancer. Results There were 88 cases (35.9%) achieved radiological complete response (rCR) and 106 cases (43.3%) achieved pCR in 245 patients. Enhanced MRI in assessing the size of residual tumors overestimated and underestimated 12.7% (31/245) and 9.8% (24/245) of patients, respectively. When setting rCR as the MRI assessment index the specificity, sensitivity and PPV were 84.2% (117/139), 62.3% (66/106) and 75.0% (66/88), respectively. When setting near-rCR as the MRI assessment index the specificity, sensitivity and PPV were 70.5% (98/139), 81.1% (86/106), and 67.7% (86/127), respectively. The positive predictive value of both MRI-rCR and MRI-near-rCR in evaluating pCR of each subtype subgroup of breast cancer was the highest in the HR–/HER2+ subgroup (91.7% and 83.3%, respectively). In each subgroup, compared with rCR, the specificity of near-rCR to predict pCR decreased to different degrees, while the sensitivity increased to different degrees. Conclusions Breast contrast-enhanced MRI can more accurately evaluate the efficacy of localized breast lesions after NAC, and can also more accurately predict the breast pCR after NAC. The HR–/HER2+ subgroup may be a potentially predictable population with pCR exemption from breast surgery. However, the accuracy of the evaluation of pCR by breast enhancement MRI in HR+/HER2– subgroup is low.