The CVD-SiC fiber was studied by using laser Raman spectra. It was found that the sharp TO peak exists in the first SiC deposit layer, indicating the larger SiC grains. But the second SiC deposit layer is with small grains. Raman peak of carbon and silicon was detected respectively in the first and second layer. Compared with that of the single SiC fiber, the TO peaks move to the high wave number for the SiC fiber in SiCf/Ti-6Al-4V composite. It indicates that the compressive thermal residual stress is present in the SiC fiber during the fabrication of the composite because of the mismatched coefficient of thermal expansion between Ti-6Al-4V matrix and SiC fiber. The average thermal residual stress of the SiC fiber in SiCf/Ti-6Al-4V composite was calculated to be 318 MPa and the residual stress in first deposit layer is 436 MPa which is much higher than that in the second layer.