An experimental study on the preparation of (Mo,Nb)Si2 ternary alloys was conducted by self-propagating high-temperature synthesis method from elemental powder compacts of different stoichiometries. And the combustion mode, combustion temperature, flame-front propagation velocity and product structure were discussed. The results show that (Mo,Nb)Si2 ternary alloys are characterized by an unsteady state combustion mode with a spiral−trajectory reaction front from top to bottom. The combustion temperature and flame−front propagation velocity decrease with the addition of coarse niobium powder. The combustion temperature and flame-front propagation velocity of MoSi2 are 1629K and 3.13mm/s respectively. However, those of (Mo0.8Nb0.2)Si2 alloy are 1460K and 1.97mm/s. The solid solubility of niobium in MoSi2 is less than 2.5at.%, and the combustion synthesis produce still remains Cllb single-phase structure in (Mo1-x,Nbx)Si2(x<0.075) sample. The C40-type structure appears in (Mo0.925,Nb0.075)Si2 compact and the intensity of diffraction peaks of C40-type phase gradually reinforces with the increase of niobium content. Combustion synthesis is an effective technology for producing (Mo,Nb)Si2 ternary alloys.