We have developed a novel rheo-optical Fourier-transform infrared (FTIR) imaging technique that can probe the molecular-scale deformation behavior of a polymer matrix in composite materials. This rheo-optical FTIR imaging is based on in situ-polarized FTIR imaging of a polymer sample while it is being deformed by mechanical force. This imaging technique readily captures the orientation of the polymer molecules resulting from the applied strain. Analysis of the resulting FTIR imaging data by disrelation mapping makes it possible to further elucidate subtle but pertinent spectral variations arising from changes in the state of molecules within the spectroscopic images. In this study, the rheo-optical FTIR imaging is applied to analysis of the deformation behaviors of a composite composed of polypropylene containing hydroxyl groups (PPOH) and silica spheres (SS) to investigate matrix-filler adhesion of the composite. Our rheo-optical FTIR imaging analysis revealed selective inhibition of PPOH orientation at the matrix-filler interface during tensile deformation due to high matrix-filler adhesion via hydrogen bonding. The strong link between the PPOH matrix and SS filler efficiently restricts mobility of the matrix, resulting in the reinforcement of PPOH by addition of SS. Rheo-optical FTIR imaging is an effective tool for probing localized deformation behavior at the matrix-filler interface as well as achieving a better understanding of the correlation between matrix-filler adhesion and the effective reinforcement of composites.