This study presents comparative assessments on hydrophilic and hydrophobic ZnO nanoparticles and their deposition methods on the surface hydrophobicity of silicone rubber (PDMS) and glass substrates. The influence on the surface hydrophobicity and wettability of all the variables regarding the deposition methodologies and the interaction of the nanoparticles with the substrates were within the scope of this study. The different surfaces created by spraying, dipping and drop-pipetting deposition methods were assessed by static contact angle measurements and contact angle hysteresis from advancing and receding angles, as well as by the calculation of the sliding angle and the surface energy parameters. An accurate methodology to determine the contact angle hysteresis was proposed to obtain repetitive and comparative results on all surfaces. All the measurements have been correlated with the morphology and topography of the different surfaces analysed by FE-SE microscopy. The spray-deposition of hydrophobic ZnO nanoparticles on PDMS resulted in super-hydrophobic surfaces, exhibiting hierarchical structures with micro-and nanometer features which, together with the low surface energy, promotes the Cassie-Baxter wetting behavior. This study provides the fundamental approach to select critically the most promising combination in terms of materials and deposition techniques to create silicone-based super-hydrophobic surfaces with potential to be applied in high voltage outdoor insulation applications.