Bulk glassy Zr55Al20–xCo25Nbx (x = 0 to 5 at.%) alloys with critical diameters of 2.5–5 mm and supercooled liquid region of 48–75 K were produced by copper-mold casting. These alloys were spontaneously passivated in 3 mass% NaCl and 1 N H2SO4 solutions. The addition of Nb to the alloy enhanced the pitting corrosion resistance in the NaCl solution and enabled the open-circuit potential in the H2SO4 solution. Zr- and Al-enriched passive films formed on the bulk glassy Zr–Al–Co–Nb alloys exposed to air and on those immersed in the solutions. The increase in Nb content of the alloys resulted in an increase in Zr and Nb concentrations and a decrease in Al concentration of the passive film. The Vickers hardness, Young's modulus, compressive fracture strength, fracture strain, and plastic strain of the bulk glassy Zr–Al–Co–Nb alloys were 550, 98 GPa, 2100 MPa, 2.9%, and 0.9%, respectively.