Molecular electronic systems have received growing interest over the last 25 years, with research addressing both fundamental questions of current transport through organic materials and the ability to tailor the surface behaviour of technologically important materials. This thesis investigates the insulating properties of alkyl monolayers on silicon surfaces and the conductivity of DNA templated molecular nanowires within lithographically formed structures. Monolayers used in this work are formed by the thermal hydrosilylation of hydrogen terminated silicon with 1-alkenes in the absence of catalysts and intermediary terminations. This route to functionalization was chosen in order to minimize the introduction of electrically active contaminations which could potentially limit the performance of alkyl films in electronic devices.