Zr-based Bulk metallic glasses exhibit incredible corrosion resistance and glass forming ability, however, these properties need further enhancement to meet the practical use. In this study, Zr63Fe2.5Cu23Al11.5, a new type of Zr-based bulk metallic glass was fabricated. Potentiodynamic polarization techniques were used to measure the corrosion resistance of this alloy. Furthermore, crystallization behavior and kinetics of Zr63Fe2.5Cu23Al11.5 bulk metallic glass were investigated by using differential scanning calorimetry of non-isothermal model. Kissinger and Ozawa methods were used for calculating activation energies of crystallization and the mechanism of crystallization was analyzed by Johnson-Mehl-Avrami-Kolmogorow methods. The results suggest that this specified metallic glass system possesses a relatively high thermal stability and glass forming ability. Moreover, the crystallization procedure is mainly dominated by nucleation with an increasing rate. The study demonstrates that the slight composition adjustment of Zr–Fe–Cu–Al system bulk metallic glass can make a considerable contribution to higher glass forming and thermal stability as well as corrosion resistance.