Raman spectroscopy was used to measure Raman spectra of the inner SiC fibers and surface C-rich layers of SiC fibers, composite precursors and SiCf/Ni-Cr-Al composites. The residual stresses of the inner SiC fibers and surface C-rich layers were calculated, and the effect of the (Al + Al2O3) diffusion barrier layer on the interfacial residual stress in the composites was analyzed in combination with the interface microstructure and energy disperse spectroscopy (EDS) elements lining maps. The results show that the existence of (Al + Al2O3) diffusion barrier improves the compatibility of the SiCf/Ni-Cr-Al interface, inhibits the adverse interfacial reaction, and relieves the residual stress inside SiC fibers and at the interface of composite material. Heat treatment can reduce the residual stress at the interface. As the heat treatment time increases, the residual stress at the interface decreases.