AbstractThe matrix/reinforcement interphase in aramid fiber/epoxy and carbon fiber/epoxy composites were modeled by coating an internal reflection spectroscopy (IRS) element with a thin layer of an aramid or of carbonized poly(acrylonitrile) (PAN). The coated element was then used as a substrate on which the curing of an epoxy resin took place. Infrared (IR) spectroscopy was used to demonstrate that the simulated reinforcement surfaces modified the crosslinking chemistry in the first 200–400 nm of epoxy matrix adjacent to the surfaces, producing an interphase of matrix material with properties different from those of the bulk of the epoxy matrix. This hypothesis was confirmed by the fabrication and testing of a series of unidirectional aramid fiber/epoxy and carbon fiber/epoxy composites.