A two-step bottom up preparation protocol is proposed as a useful tool for the controlled modification of tin oxide films by means of Pd nanoparticles (PdNPs). Colloidal palladium is prepared via an electrolytic process that affords for a core-shell particle structure, while nanostructured tin oxide films are prepared following a sol–gel process. Pd/SnOx composite layers are obtained adding a proper aliquot of pre-formed PdNPs to the tin oxide precursor solution. The nanomaterials surface chemical composition is addressed by X-ray Photoelectron Spectroscopy. Preliminary results on the application of Pd/SnOx as active layers in chemiresistor-type gas-sensing devices are reported, as well.