Pyroelectric Langmuir-Blodgett (LB) films of calix[8]arene have been prepared using the alternate-layer technique. The technique allows the co-deposition of carboxyl and amino-substituted calix[8]arenes, and results in the alternating acid/amine/acid... layer structure. A pyroelectric coefficient of up to 15 μC m - 2 K - 1 has been obtained from a 13 alternate layer t-butyl calix[8]arene LB film. The pyroelectric response of this system has been shown to remain constant over ~5000 continuous heating and cooling cycles. The introduction of metal ions into the LB matrix dramatically increases the temperature range over which the pyroelectric activity can be measured.