Breast cancer is one of the leading cancers in women worldwide. Notwithstanding the clear advances being made in treatment, early diagnosis of the disease can certainly be expected to reduce morbidity and mortality. With increasing evidence of the role of epithelial to mesenchymal transition (EMT) in tumour progression, early detection of this phenomenon is suggested to be important given that the majority of breast cancer deaths are due to tumour invasion and metastasis. Although histopathology and biomedical imaging techniques continue to be used as standard procedures in breast cancer diagnosis, these techniques have a number of disadvantages, including being time‐consuming, the imaging in particular having attendant limited resolution, sensitivity, and specificity, leading to results that are prone to errors in human interpretation. Due to its rapidity and high specificity, Raman spectroscopy has emerged as a diagnostic tool for breast cancer, useful in identifying malignancy of breast cells, correlated with the EMT phenotype, expressed at the molecular level. Detailed biochemical information from tissue biopsies can also be provided from use of this technique. The use of Raman spectroscopy in breast cancer investigations over the past 10 years and more, including in the study of EMT, is reviewed in the present work also listing the corresponding Raman peaks reported in the literature in seeking to better facilitate identification of peaks of interest.