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 mu C 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 similar to 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.