A new series of organometallic/inorganic composite Langmuir-Blodgett (LB) films consisting of a rigid-rod polyplatinyne polymer coordinated with 2,7-bis(buta-1,3-diynyl)-9,9-dihexylfluorene (denoted as PtP) as the pi-conjugated organometallic molecule, an europium-substituted polyoxometalate (POM; POM = Na9EuW10O36, K-13[Eu(SiW11O39)(2)] and K-5[Eu(SiW11O39)(H2O)(2)]) as the inorganic component, and an amphiphilic behenic acid (BA) as the auxiliary film-forming agent were prepared. Structural and photophysical characterization of these LB films were achieved by pi-A isotherms, absorption and photoluminescence spectra, atomic force microscopy imaging, scanning tunneling microscopy, and low-angle X-ray diffraction. Our experimental results indicate that stable, well-defined, and well-organized Langmuir and LB films are formed in pure water and POM sub-phases, and the presence of Eu-based POM in the subphase causes an area expansion. It is proposed that a lamellar layered structure exists for the PtP/BA/POM LB film in which the POM and Ptp molecules can lay down with the interfacial planes. Luminescence spectra of the prepared hybrid LB films show that near-white emission spectra can be obtained due to the dual-emissive nature of the mixed PtP/POM blends. These Pt-polyyne-based LB films displayed interesting electric conductivity behavior. Among them, PtP/BA/POM 13-layer films showed a good electrical response, with the tunneling current up to +/- 100 nA when the voltage was monitored between -1 and 7 V. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 879-888, 2010