In this study bulk metallic glass alloys in the Fe-Zr-B-M (M=Al, Co, Cu, Mo, Ni, W) systemwere produced by using a centrifugal casting method. The thickness ofthe samples that could be produced with an almost completely amorphousstructure was found to be as high as similar to2 mm for alloy Fe60Co8Zr10Mo5W2B15. Alloying element additions or replacements have resulted in a considerable effect on glass-forming ability. Among others, Al and Cu were found to have the most deteriorative effects. The ternary alloy Fe70Zr10B20, from which bulk metallic glass alloys can be formed by cleverly implementing several alloying elements, was seen to have a different phase transformation behavior when compared to alloy Fe60Co8Zr10Mo5W2B15. For the latter alloy, the phase transformation process and microstructure evolution were found to be extremely sensitive to variation of the cooling rate.