Self-assembled layers of aminosilane have been used to bind nanoparticle catalysts for electroless deposition on silicon wafers. However, the influence of accessible amino groups on aminosilane on the adhesion of nickel-phosphorus (Ni–P) deposits has not yet been determined. In this study, we deposited (3-aminopropyl)trimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and 3-(trimethoxysilylpropyl)diethylenetriamine as coupling layers between Ni-P films and silicon substrates. We explored the influence of different aminosilanes on the distribution of the catalysts and the adherence of electroless Ni-P films. The surface morphology, composition, and hardness of Ni-P films formed on the different aminosilanes were thoroughly examined. The results indicate that 3-(trimethoxysilylpropyl)diethylenetriamine can bind to the largest number of nanoparticles, but the lack of anchoring sites and catalyst aggregation accounted for the poor adhesion of the Ni-P film deposited on it.