In this contribution, we present a three-step pathway to produce a novel fiber coating, study its embedding in epoxy resin and characterize its nanomechanical properties at the interface between fiber and matrix. Inorganic surfaces were sulfhydrylated for subsequent use in thiol-initiated ene photopolymerization. The influence of water on the sulfhydrylation process was studied to find conditions allowing monomolecular deposition. Surface morphology as well as SH-content were evaluated by UV/vis spectroscopy, atomic force microscopy and spectroscopic ellipsometry. Brush-like polymer layers (PS and PMMA) were introduced by UV-light initiated surface polymerization of vinyl monomers. Polymer growth and morphology were studied. After embedding, the nanomechanics of the interfacial region of the fibers was studied. AFM force spectroscopy allowed the mapping of the stiffness distribution at the cross-section of the composite with high spatial resolution. Elastic moduli were determined by Hertzian contact mechanics. The individual phases of the composite material (fiber, interphase, and matrix) can be clearly distinguished based on their mechanical response. The synthesis, morphology, and mechanical properties of an interphase based on a polymeric graft-film swollen with matrix material are shown, and perspectives of these novel coatings for improved matrix-fiber compatibility and interfacial adhesion are discussed.