Metallic nanoparticles (MNP) are utilized as electrocatalysts, cocatalysts, and photon absorbers in heterostructures that harvest solar energy. In such systems, the interface formed should be stable over a wide range of pH values and electrolytes. Many current nonthermal processing strategies rely on physical interactions to bind the MNP to the semiconductor. In this work, we demonstrate a generic chemical approach for fabricating highly stable electrochemically/photocatalytically active monolayers and tailored multilayered nanoparticle structures using azide/alkyne-modified Au, TiO2, and SiO2 nanoparticles on alkyne/azide-modified silicon, indium tin oxide, titania, stainless steel, and glass substrates via click chemistry. The stability, electrical, electrochemical, and photocatalytic properties of the interface are shown via electrochemical water splitting, methanol oxidation, and photocatalytic degradation of Rhodamine B (RhB) dye. The results suggest that the proposed approach can be extended for the large-scale fabrication of highly stable heterostructure materials for electrochemical and photoelectrocatalytic devices.