Based on the repeatability and good biological compatibility two-dimensional nano silver membrane as oxyhemoglobin near infrared surface enhanced Raman scattering(SERS), a study on oxyhemoglobin used SERS spectra was carried out by using near infrared laser with good match as excitation light source, which caused resonance Raman effect respectively of healthy women and women with breast cancer. The study found that obvious differences existed between healthy women and female breast cancer patients′ oxyhemoglobin. By using the method of principal component analysis(PCA) and independent variable T test statistical analysis through SPSS, an extremely significant difference was found between the two spectra in 659, 813 and 1122 cm-1 Raman shift spectrum peak. By attribution analysis on the principal component, a significant reduction was found, compared with the healthy women, in the female breast cancer patients′ oxygenated hemoglobin molecules, pyrrole ring vibration, and symmetric deformation of antisymmetric deformation and pyrrole ring breathing vibration intensity, which resulted in an obvious difference in the graph spectral peaks. In addition, SERS technique can be combined with SPSS statistical analysis method to distinguish the oxygenated hemoglobin between healthy women and patients with breast cancer, which is expected to develop into a new type of clinical diagnosis technology for breast cancer.