Nanoscale hybrid organic/inorganic Langmuir-Blodgett films of cerium-substituted heteropolymolybdates(Ce-HPMo) and π-conjugated macromolecule poly(1,2-dihydro-2,2,4-trimethyl)quinoline(PQ) were obtained with auxiliary film-forming material stearic acid(SA) or octadecylamine(ODA). The surface pressure-area isotherms illuminate the formation of the hybrid LB films of PQ/ODA/Ce-HPMo and P Q/SA/Ce-HPMo. The different film-forming mechanism was discussed when the different auxiliary film-forming materials were used in the system. The absorption spectra indicate that the molecules of PQ and Ce-HPMo are incorporated into the LB films. Tapping-mode AFM image reveals a granular surface texture of nanosized Ce-substituted heteropolymolybdate. STM image shows that the conductivity is greatly improved after Ce-substituted heteropolymolybdates are incorporated in the films.