The pyroelectric properties of the solid mixtures of achiral liquid crystalline polymers with their monomers were studied. The composites were fabricated in a thin film form (less than 1 μm) by spin-coating technique. The maximum value of the current responsivity being 0.67 μA/W has been obtained for optimum monomer/polymer ratio of 33%:67% by weight. The pyroelectric voltage was measured in the frequency range from 10 Hz up to 250 kHz. The figure of merit for the composite at room temperature is about 0.8 nC/cm2 K, which is more than twice higher than that of polyvinylidene fluoride with trifluroethylene 70%:30%.