The Fourier transform infrared (FTIR) spectroscopic studies of the poly(styrene-co-acrylonitrile) (SAN) and poly(vinyl chloride-co-vinyl acetate) (VYHH) blends produced by different blending techniques, viz., solution blending, melt-blending, and also the co-precipitation methods of blending, were performed. In the case of miscible blend systems, substantial band shiftings took place, whereas immiscible blend systems showed slight or no band shifting. The miscible blends showed a substantial residual spectrum which was absent in the case of the immiscible system when a similar subtraction process was carried out.