Ag₂O-Ag-PSi (porous silicon) surface-enhanced Raman scattering (SERS) chip was successfully synthesized by electrochemical corrosion, in situ reduction and heat treatment technology. The influence of different heat treatment temperature on SERS performance of the chip is studied. The results show that the chip treated at 300 °C has the best SERS performance. The chip was composed of Ag₂O-Ag nano core shell with a diameter of 40–60 nm and porous silicon substrate. Then, the optimized chip was used to perform SERS test on serum samples from 30 healthy volunteers and 30 early breast cancer patients, and the baseline was corrected by LabSpec6 software. Finally, the data were analyzed by principal component analysis combined with t-distributed Stochastic Neighbor Embedding (PCA-t-SNE). The results showed that the accuracy of the improved substrate combined with multivariate statistical method was 98%. The shelf life of the chips exceeded six months due to the presence of the Ag₂O shell. This study provides a basis for developing a low-cost rapid and sensitive early screening technology for breast cancer.