Ni-and Cu-free Zr-Al-Co-Nb glassy alloys with different Nb and Co contents were synthesized by melt spinning and copper mold casting. The effects of Nb addition to partially replace Co in the Zr 55 Al 20 Co 25 glassy alloy on the glass-forming ability, thermal properties, in-vitro biocorrosion behavior and surface wettability of the metallic glasses were investigated. Although addition of Nb up to 5 at.% slightly decreased the supercooled liquid region and the glass-forming ability (GFA), the alloys could be casted in a bulk glassy rod form with diameters up to 3 mm. The Zr-Al-Co-Nb glassy alloys were spontaneously passivated with low passive current densities in phosphate buffered saline and Hanks' solution. Substitution of "toxic" Co by Nb is effective in improved the corrosion resistance of the Zr-Al-Co glassy alloy. Water contact angle measurements showed that Nb addition increased the hydrophilicity of the glassy alloys, which may enhance cell adhesion of the alloys in biomedical applications. Because of the lack of long-range atomic order, Zr-based bulk metallic glasses (BMGs) exhibit superior strength, high elastic strain limits and fatigue endurance limits, relatively low Young's modulus, and excellent wear and corrosion resistance [1][2][3][4][5], which attracted attention in biomedical applications. However, toxic elements such as nickel and copper are often included in Zr-based metallic glasses to achieve high glass-forming ability (GFA), which are thought to impair cellular metabolism [6]. In recent years, many efforts have been made to remove these elements from Zr-based BMGs to further improve their biocompatibility. (x = 2.5 at.% and 5 at.%) metallic glasses have been developed, and addition of Nb were found to enhance their resistance to pitting corrosion in 3 mass% NaCl solution [20]. From the viewpoint of biomedical engineering, Nb is recognized as a highly biocompatible element. In the quaternary Zr-Al-Co-Nb alloys, Co is more cytotoxic than Al, and excessive amounts of Co or prolonged exposure to Co may result in Co poisoning [21][22][23]. Therefore, rather than substitution of Al with Nb as in the previous study [20], substitution of Co with Nb could further improve the biocompatibility of the alloys. In consideration of potential medical applications, the GFA and in vitro biocorrosion behavior of Zr 55 Al 20 Co 25x Nb x glassy alloys were investigated in the present work. Surface wettability of the