The electron transfer through an organized organic monolayer of alkyl chains adsorbed on a silicon wafer has been studied. The silicon was used as an electrode in a three-electrode electrochemical cell, and the current versus voltage response was measured. The results show that when the chains in the monolayer are in the "all trans" configuration, the charge transfer efficiency is higher than when the chains have a "gauche" configuration. A mechanism rationalizing all the observations is suggested.