The need for sustainable energy solutions is steering research towards green fuels. One promising approach involves electrocatalytic gas conversion, which requires efficient catalyst surfaces. This study focuses on developing and testing a hydrophobic octadiene (OD) coating for potential use in electrocatalytic gas conversion. The approach aims to combine a plasma-deposited hydrophobic coating with air-trapping micro- and nanotopographies to increase the yield of electrocatalytic reactions. Plasma polymerisation was used to deposit OD films, chosen for their fluorine-free non-polar properties, onto titanium substrates. We assessed the stability and charge permeability of these hydrophobic coatings under electrochemical conditions relevant to electrocatalysis. Our findings indicate that plasma-deposited OD films, combined with micro-texturing, could improve the availability of reactant gases at the catalyst surface while limiting water access. In the presence of nanotextures, however, the OD-coated catalyst did not retain its hydrophobicity. This approach holds promise to inform the future development of catalyst materials for the electrocatalytic conversion of dinitrogen (N₂) and carbon dioxide (CO₂) into green fuels.