The pyroelectrical activity in copolysiloxane/eicosylamine alternate layer Langmuir-Blodgett (LB) films incorporating Cd2+ and Mn2+ ions is reported. The pyroelectric coefficients and dielectric constants have been measured in order to determine the figure of merit in the context of thermal imaging materials. The pyroelectric results indicate that cadmium ion incorporation leads to a significantly improved performance compared to the system without metal ions. Additionally, preparation of LB films using a metal-doped subphase leads to an extended operating temperature range for the fabricated pyroelectric devices.