Non-electroactive alkanethiolate monolayers containing internal amide bonds were used as model systems for the studies of the effect of structure of the intervening medium on long-range electron transfer. The blocking properties and the kinetics of electron transfer across the monolayers immobilized on gold were studied by voltammetry with the hexachloroiridate(IV) ion as the redox probe in the solution. The electron transfer efficiency was measured over a large potential window. The three types of monolayers studied were simple octadecanethiol and two amide-containing systems with one or two amide moieties in place of selected methylene groups in the main alkyl chain. Enhanced electronic coupling between the redox probe and the metal of the electrode was found for the monolayers with internal amide bonds. We ascribed it to the contribution of a hydrogen bonded network to electron tunneling through the monolayer. in the case of monolayers formed by molecules containing two secondary amide groups, the location of amide moieties inside the monolayer was shown to,play an important role in the electron transfer efficiency. The second amide moiety placed in the alkyl chain in the odd position relative to the first amide did not increase electronic coupling in the monolayer. This behavior can be explained as due to larger distances between the amide groups in the external plane of the monolayer leading to difficulty in the formation of the hydrogen bond network. The position of the amide group relative to the electrode surface may be also considered as an important factor determining the efficiency of electron tunneling through the monolayer.