In recent years, more and more emphasis has been placed on the development and functionalization of metallic substrates for medical applications to improve their properties and increase their applicability. Today, there are many different types of approaches and materials that are used for this purpose. Our idea was based on a combination of a chemically synthesized Ag-SiO2 nanocomposite and the electrophoretic deposition approach on a NiTi shape memory substrate. As a result, silver-silica coating was developed on a previously passivated alloy, which was then subjected to sintering at 700 °C for 2 h. The micrometer-sized coat-forming material was composed of large agglomerates consisting of silica and a thin film of submicron- and nano- spherical-shaped particles built of silver, carbon, and oxygen. Structurally, the coatings consisted of a combination of nanometer-sized silver-carbonate that was embedded in thin amorphous silica and siloxy network. The temperature impact had forced morphological and structural changes such as the consolidation of the coat-forming material, and the partial coalescence of the silver and silica particles. As a result, a new continuous complex ceramic coating was formed and was analyzed in more detail using the XPS, XRD, and Raman methods. According to the structural and chemical analyses, the deposited Ag-SiO2 nanocomposite material’s reorganization was due to its reaction with a passivated TiO2 layer, which formed an atypical glass-like composite that consisted of SiO2-TiO2 with silver particles that stabilized the network. Finally, the functionalization of the NiTi surface did not block the shape memory effect.