A SAM-LB composite film containing azobenzene chromophore was fabricated on gold by combining the self-assembled monolayer (SAM) technique and the Langmuir-Blodgett (LB) technique. Reflection absorption FTIR studies indicate that the composite film has an ionic bonding character at the SAM-LB interface, which has greatly improved the film stability and effectively prevented the destructive intermolecular aggregation, as evidenced by atomic force microscopy observations. The relatively loose packing structure provides enough free volume to undergo a reversible trans-cis photoisomerization and thus enabled us to perform the electrochemical studies of the cis-azobenzene redox group in such organized monolayer assemblies. The cis-azobenzene SAM-LB composite film shows a stable and clearcut Faradaic response within the pH range 3.0-9.0, attributable to the 2e(-) and 2H(+) electrochemical reduction-oxidation of cis-azobenzene/hydrazobenzene. Comparing with the trans-azobenzene composite film, the LB films deposited on SnO2, and the azobenzene-functionalized thiolate SAMs on gold, its reaction kinetics is more reversible as seen from the larger electron-transfer rate constant, smaller peak-to-peak splitting, and smaller half-peak width. The logarithmic rate constant shows a complicated but unique pH dependence, characteristic of azobenzene redox kinetics, which is explained by the varied sequences of electron transfers and protonations in different pH ranges.