This paper describes an attempt to correlate the nature of polar-polar interaction between the reinforcement and matrix in a polymer composite with the boundary phase structure formed in contact with the reinforcement. It is shown by analyzing the mechanical dispersion data that the reinforcement-matrix interaction of Kevlar fiber reinforced poly(hydroxypropyl ether of bisphenol A) (P) is increased by blending poly(ethylene oxide) (E) or poly(ethylene adipate) (A) as a part of matrix, and that E is more efficient than A for the increase of the interaction. These results can be supported at the molecular level from the inspection of the Fourier transform infrared spectra on the Kevlar fiber coated with matrix polymers and the mixture of matrix polymers with benzanilide, which is used as a model compound of Kevlar fiber. It can be shown from the electron spectroscopy for chemical analysis on the films of PIE and P/A blend polymers formed on nylon 6 substrate (N), which is also used as a model material for the reinforcement, that A concentrates on the N-facing side for P/A film and that E concentrates on the air-facing side for PIE film. This result indicates the different susceptibility between P/A and PIE blends to the surface force from N, and hence, it likewise indicates the different interaction with the reinforcement in each blend, as shown by the mechanical dispersion data.