Composite monolayers of cadmium stearate and polyaniline processed with camphor sulphonic acid have been obtained at the air–water interface and subsequently transferred onto substrates as uniform Langmuir–Blodgett multilayers. Pressure–area (Π-A) isotherm studies indicated that polyaniline molecules are not squeezed out of the cadmium stearate matrix during compression or in the compressed state. Monolayer stability is seen to decrease when the polymer content is increased beyond 60% (in weight) which is probably associated with the formation of microaggregates that also affected the monolayer surface potential at large areas per molecule. With increasing amount of polyaniline in the mixture, a transition from Y-type to Z-type deposition has been observed. Transferred multilayer LB films were characterized by UV-vis, FTIR, XRD, surface potential, and dc electrical conductivity measurements. UV-vis results indicated that though the polyaniline was in the doped state in the spreading solution, the transferred films were in the emeraldine base state. FTIR studies revealed that the transferred films mainly contained cadmium stearate salt in addition to polyaniline. XRD results indicated that the stacking order is dependent on the polyaniline content in the composite films, the order was found to decrease upon increasing the polymer amount. The uniformity of transferred films was confirmed by surface potential studies. A possible packing arrangement in these composite Langmuir and Langmuir–Blodgett films has been proposed.