This article deals with the materials science and engineering of glass-forming alloys in Fe-(Nb)-(Al, Ga)-(P, C, B, Si), Fe-(Cr, Mo, Ga)-(P, C, 13) and Fe-(Co, Ni)-(Cu)-(Zr, Nb)-B bulk metallic glasses (BMG) systems with high thermal stability of the undercooled melt against crystallization. Different liquid quenching techniques (melt-spinning or copper-mold casting) as well as hot pressing of the powder obtained by milling of the melt-spun ribbons were used to prepare samples in various shapes. Synthesis of the investigated BMG alloys is discussed according to Inoue's empirical components rules for the achievement of the large glass forming ability (GFA). Thermal and microstructure characterization (performed by DSC, TMA, XRD and Mossbauer spectroscopy) was used to correlate GFA, mricrostructure and thermo/thermo-magnetic treatments with optimum soft magnetic properties.