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Natural polyphenols are known for their variety of pharmacological properties including chemosensitizing of anticancer drugs. A dietary polyphenol, ferulic acid, was observed for the first time enhancing epirubicin-induced apoptosis in MDA-MB-231 human breast cells via the endoplasmic reticulum (ER) stress pathway. The combined index of 10 μM ferulic acid and epirubicin was less than 0.9, which indicates ferulic acid could significantly enhance the sensitivity of MDA-MB-231 cells to epirubicin. Flow cytometry analysis showed that apoptosis by epirubicin (1 μM) in MDA-MB-231 cells was enhanced by ferulic acid (10 μM). Western blot analysis demonstrated apoptosis was induced by increasing the expression of Bax, downregulating the level of Bcl-2 and activating caspase-3. Furthermore, it was observed that the synergism of ferulic acid (10 μM) and epirubicin (1 μM) increased the expression levels of the ER stress-related proteins such as PDI, IRE1α and PEPK while the results should be opposite after using the ER stress inhibitors. In conclusion, our results indicate that ferulic acid could be served as a potential officinal adjuvant for breast cancer treatment.