Binary β-FeSi2 phase is an important semiconductor metal silicide with narrow band-gaps. The formation of this phase in ternary alloys was investigated for the search of ternary semiconductor silicides. Using the cluster line approach as the theoretical guideline, a structure model is established with one cluster and one glue atom, and alloy series of Fe3Si8M(M=B, Cr, Ni, Cu, Co, Al) were designed by replacing the glue atom Fe in binary β-FeSi2. To obtain homogenous alloys, high vacuum suction casting and melt spinning method were used for the preparation of alloy rods and ribbons. Microstructure and composition analysis showed that the β phase could dissolve 15%—20% Ni, 4%—13% Cu, 7%—10%Co and 7%—10%Cr (molar content). However, in contrary to the designed formula, the added Al replaces Si rather than Fe. There were trace amounts of amorphous particles in Fe3Si8B and Fe3Si8Cr ribbon samples, which showed under the rapid cooling conditions, the addition of B and Cr was favorable for the amorphous phase formation.