A Zr65Al7.5Ni10Cu17.5-xPd x (x=0-17.5 at. %) alloy system is found to exhibit a unique dependence of glass-forming ability (GFA) on casting atmosphere during mold-casting process. High-Pd containing alloys (x=7.5-17.5) showed a remarkable increase of critical size (dc) for glass formation, in contrast with the low-Pd containing alloys (x=0-5) in which no significant change in d c was observed, as the pressure of Ar atmosphere varied from vacuum to ambient. The origin of the phenomenon has been successively unveiled by correlating the cooling characteristic during casting process and phase transformation behavior during continuous cooling of the alloy system. The consequence in the structure and property control is investigated and discussed in detail.