Non-centrosymmetric Langmuir–Blodgett (LB) thin films exhibit a temperature-dependent electric polarisation, which is known as the pyroelectric effect. Alternate layer LB films were prepared by transferring polysiloxane alternately with eicosylamine from a subphase of Millipore water (18 MΩ cm − 1 ) incorporating different metallic ions onto a 50 nm thick thermally evaporated aluminium substrate. Pyroelectric and dielectric measurements were performed on LB films with a sandwich structure comprising film. Pyroelectric coefficients of these LB films are measured at several temperatures. The dielectric constant and dielectric losses were obtained to determine the pyroelectric figure of merit values of these LB films, which were calculated in the range of 24.9 to 56.7 μC m − 2 K − 1 .