The effects of compound silicate gangue on mineral composition and microstructure of sinter produced by Baiyunebo iron ore concentrates was studied by using mini-sintering test device and optical microscope. The result showed that compound silicate gangue has lower melting point, wider melting temperature range, longer melting time and melts easily to form glassiness during the sintering process. It can promote the solution of CaO and CaF2 in glassy phase, which affects viscosity and fluidity of glassy phase as well as the homogeneity of sinter microstructure. The compound silicate gangue intensely inhibits the generation of complex calcium ferrite and cuspidine as well. The major mineral compositions of sinter are hematite and glassy phase. The sinter exhibits multi-cavities and grainy structure when SiO2 exists entirely in the form of compound silicate gangue.