We describe the possibility of using γ-aminopropyltriethoxysilane (γ-APS) to increase the durability of epoxy powder coating/steel joints. The curing temperature of epoxy powder coatings is frequently above 200 °C, which is seen so far as a major limitation for the use of the heat-sensitive aminosilane coupling agent. Despite this limitation, we demonstrate that aminosilane is a competitive alternative to traditional chromate conversion to enhance the durability of epoxy powder coatings/steel joints. Fourier-transform reflection-absorption infrared spectroscopy (FT-RAIRS), X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) were used to identify the silane deposition conditions that influence the adhesion of epoxy powder coatings on steel. We show that AFM analysis provides highly sensitive measurements of mechanical property development and, as such, the degree of condensation of the silane. The joint durability in water at 60 °C was lower when the pH of the γ-APS solution was controlled at 4.6 using formic acid, rather than that at natural pH (10.6). At the curing temperature of 220 °C, oxidation of the carbon adjacent to the amine headgroup of γ-APS gives amide species by a pseudofirst-order kinetics. However, a few amino functionalities remain to react with oxirane groups of epoxy resin and, thus, strengthen the epoxy/silane interphase. The formation of ammonium formate in the acidic silane inhibits the reaction between silane and epoxy, which consequently decreases the epoxy/silane interphase cohesion. We find that the nanoroughness of silane deposits increases with the cure temperature which is beneficial to the wet stability of the epoxy/steel joints, due to increased mechanical interlocking.