Two-dimensionally cross-linked ultrathin films of poly(maleic acid-alt-methyl vinyl ether) (MA-MVE) and poly(allylamine) (PAA) were produced by using sodium dioctadecyl sulfate (2C18S) as the monolayer template for Langmuir-Blodgett (LB) depositio n. The template molecules were subsequently removed by thermal treatment followed by extraction. The polyion-complexed monolayers of three components, i.e., template 2C18S, co-spread PAA, and subphase MA-MVE, were formed at the air-water interface. Their monolayer properties were studied by the surface pressure-area isotherm. The monolayers were transferred on solid substrates as Y type. The polyion-complexed LB films and the resulting network films were characterized by FT-IR spectroscopy, X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The cross-linking to form a polymer network was achieved by amide or imide formation through heat treatment under a vacuum. SEM observation of the film on a porous fluorocarbon membrane filter (pore diameter 0.1 ㎛) showed covering of the pores by four layers in the polyion complex state. Extraction by chloroform followed by heat treatment produced hole defects in the film.