Two methods, Langmuir-Blodgett (LB) and self-assembly (SA), were used in the present work to fabricate certain interfacial structures for the study of long-range electron transfer. We have successfully constructed two different 'bridges' for the interfacial electron transfer in azobenzene LB/SAM composite bilayer systems. One has ionic bonding character, while the other has face-to-face hydrogen bonding at the interface of an ABD (4-octyl-4'-(3-carboxy-trimethylene-oxy)-azobenzene) LB monolayer and the underlying aminothiol SAM. These structures have been confirmed by using RA-FTIR and contact angle titration. Furthermore, the apparent electron transfer rate across the ionic bonding 'bridge' is much more rapid than in the hydrogen-bonded case, indicating that the interfacial structure plays a crucial role in the long-range electron transfer kinetics.