We have shown that plasma polymerisation can be used as a method for the ordered growth of monolayer films that are otherwise challenging to deposit. An analysis of the early stages of plasma polymer film growth confirms a significant surface dependence in the first 30 nm of growth, beyond which molecular films converge to a flat uniform coating. Through an investigation of the stable free radical TEMPO molecule, we have found that plasma polymerisation followed by a sample annealing process results in a stable, ordered monolayer film where TEMPO molecules are predicted to adopt an antiparallel arrangement with up to 50% of the functional NO groups aligned perpendicular to the surface. These results provide new insights into the importance of the early stages of plasma polymer film formation and provide new routes for the development of anti-biofouling polymer coatings.