LB films of organic-inorganic charge-transfer systems, Cu-complexes of 2-methyl-5-octadecyIDCNQI(C18MeDCNQI) and 2-alkylTCNQ(CnTCNQ with n=12,15 and 18), were successfully fabricated by utillizing the airwater interface as a reaction field for the reduction of the acceptor moieties. The charge transfer degrees of the C18MeDCNQI and CnTCNQ in the LB films were estimated at -1, respectively, from the changes in their IR absorption spectra upon the reduction. The molecular orientation in the films were discussed on the basis of polarized IR spectroscopy. It is suggested that the molecular orientation in the present LB films is largely affected by the coordinate bonds between the Cu cations and the cyanic groups.