Poly(amic acid) composite films with the thermotropic liquid crystal, 10-cholesteroxy-10-oxocaproic acid (COOA) were developed. The composites could still show liquid crystal behavior at low COOA loading (as low as 3 wt%) due to the phase separation under the induction of temperature. The synergistic reaction of the interaction of PAA with COOA and the arrangement of COOA endowed the films with strong fluorescence and a higher temperature shifted liquid crystal phase. Even more, the dielectric constant of the composites was enhanced. The composites were multifunctional optical-electric materials.