The corrosion resistance and biocompatibility of a novel Fe50Cr18Mo10C20Si2 metallic glass (Fe–MG), are studied by electrochemical measurements and indirect contacting cytotoxicity assays for biomedical applications. In Hank’s solution, the Fe–MG shows better corrosion resistance than SS316L, evidenced by the larger polarization resistance in the potentiodynamic and electrochemical impedance spectroscopy (EIS) tests, and the lower amounts of released metallic ions during the immersion test. X-ray photoelectron spectroscopy (XPS) analyses show that a double-layer passive film, consisting of outer Fe-rich oxide and inner Cr-rich oxide, is formed on the Fe–MG. The stable passive film, together with the defect-free nature of the metallic glass, accounts for good corrosion resistance. In addition, in vitro tests suggest that the Fe–MG extracts have good blood compatibility, and no cytotoxicity to murine fibroblast cells. Compared with other Fe-based metallic glasses, the prepared novel Fe–MG contains no toxic elements, and shows a low corrosion rate.