We have studied the interface electronic structure of transition metal film (Cr, Fe)/6H(4H)-SiC (substrate) contact systems by using soft X-ray fluorescence spectroscopy (SXFS). SXF spectra include information about either elements or symmetry of a wave function. SXFS using synchrotron radiation is a very powerful tool to search nondestructive buried interface and surface layer analysis of a thin-film on substrate contact system. Specimens of Cr(50nm)/6H-SiC(0001)Si face contact system were annealed at 750similar to950degreesC for 30 min in an electric furnace with flowing hydrogen and nitrogen gases. The Si L-2,L-3 SXF spectrum obtained from a sample annealed at 750degreesC indicates an interface electronic structure composed with the compound of Cr3Si silicide and other materials, e.g., a ternary compound. The C Kalpha fluorescence spectrum shows a signal of SiC with a posible contribution of Cr3C2 without graphite. Specimens of Fe(50nm)/4H-SiC(0001)Si face contact system were also similarly annealed at 650similar to900degreesC for 30 min. The Si L-2,L-3 fluorescence spectra can be explained by considering formation of iron silicides. Also, the C Kalpha fluorescence spectrum shows the existence of graphite-like carbon.