Dense, homogeneous, and complete self-assembled monolayers (SAMs) with epoxy surface groups were fabricated from epoxysilanes to serve as a template for chemical anchoring of polymer layers. A combination of scanning probe microscopy, ellipsometry, XPS, X-ray reflectivity, and contact angle measurements was used to study their morphology and surface properties. Self-assembly of epoxysilane molecules resulted in the formation of homogeneous SAMs 0.85 nm thick with the surface roughness 0.22 nm. Epoxysilane SAMs were tl truly monomolecular films with a virtually normal molecular orientation of densely packed molecules, which were firmly attached to the substrate. The formation of stable polymer layers from carboxy-terminated polystyrenes on reactive SAM surfaces was demonstrated.