Physicochemical analyses of Au nanoparticle monolayer formation on a glass surface functionalized with 3-aminopropyltrimethoxysilane (APTMS) and ethyltrimethoxysilane (ETMS) were performed for fabricating a nanoarchitecture of metal nanoparticles using self-assembly. The Au nanoparticle surface density on the functionalized glass surface correlated linearly with the optical response because of Au-nanoparticle localized surface plasmon resonance (LSPR). This relation enabled assessment of the Au nanoparticle deposition. A Frumkin isotherm showed the deposition of Au nanoparticles on the APTMS or APTMS/ETMS functionalized glass surface. For an APTMS-derivatized surface, the affinity between the Au nanoparticles and the surface decreased with the lowering of the APTMS surface coverage. The interaction parameter exhibited attractive interaction of 30-nm-diameter Au nanoparticles; 12 nm particles were repulsive. Adsorption isotherm experiments using Au nanoparticles on glass surfaces with an APTMS and ETMS mixed layer suggest that hydrophobic interaction between Au nanoparticles' bare gold surfaces caused the attractive interaction among 30-nm-diameter nanoparticles.