Siloxane/oxide hybrids have attracted growing attention thanks to their ability to modulate the surface energy, wettability, or self-lubricity of a material. Here, we compare two functionalisation procedures (chemical vapour deposition and wet impregnation) on substrate films composed by preformed oxide particles. Three kinds of particles, characterised by different natures (SiO2 and TiO2) and average particle size, were studied to highlight possible effects related to the chemical and morphological state of the substrate surface. Morphological characterisations were carried out using dynamic light scattering and scanning electron microscopy, while the structure of the hydrophobing layer was studied by combining Fourier transform infrared spectroscopy and solid-state nuclear magnetic resonance. The degree of functionalisation and the features of the siloxane layer vary significantly among the adopted oxides and functionalisation methods. The wettability features of the different hybrids closely mirror the results of the spectroscopic characterisations, giving rise to either Lotus leaf or patch-wise hydrophobic systems depending on the adopted conditions.