Silver nanocubes were synthesized by the polyol method and immobilized on a surface in a simple approach using an aminopropyltriethoxysilane (APTES). The optical and structural properties of the polyvinylpyrrolidone (PVP) stabilized nanocubes were investigated in solution and on glass surfaces. The SERS enhancement factors at two excitation wavelengths for crystal violet were compared with electric fields arising in different nano¬particle configurations using finite-difference time-domain simulations. They are in agreement with the preferred face-to-face orientation in the nanoaggregates on the surfaces. The facile immobilization enables on-demand preparation and use of the nanocubes in real analytical applications