The presence of axillary lymph nodes metastases in breast cancer is the most significant prognostic factor, with a great impact on morbidity, disease-related survival and management of oncological therapies; for this reason, adequate imaging evaluation is strictly necessary. Physical examination is not enough sensitive to assess breast cancer nodal status; axillary ultrasonography (US) is commonly used to detect suspected or occult nodal metastasis, providing exclusively morphological evaluation, with low sensitivity and positive predictive value. Currently, sentinel lymph node biopsy (SLNB) and/or axillary dissection are the milestone for the diagnostic assessment of axillary lymph node metastases, although its related morbidity. The impact of magnetic resonance imaging (MRI) in the detection of nodal metastases has been widely investigated, as it continues to represent the most promising imaging modality in the breast cancer management. In particular, diffusion-weighted imaging (DWI) and apparent diffusion coefficient (ADC) values represent additional reliable non-contrast sequences, able to improve the diagnostic accuracy of breast cancer MRI evaluation. Several studies largely demonstrated the usefulness of implementing DWI/ADC MRI in the characterization of breast lesions. Herein, in the light of our clinical experience, we perform a review of the literature regarding the diagnostic performance and accuracy of ADC value as potential pre-operative tool to define metastatic involvement of nodal structures in breast cancer patients.