Two kinds of liquid crystalline (LC) supramolecules with anisotropic fluorescence emission were prepared by ionic self-assembly from a copolymer, derived from acrylic acid and 6-(4′-cyanobiphenyl-4-yloxy)hexyl acrylate, and oppositely charged fluorescent molecules: stilbene-based rod-like dye (Stil) or tetraphenylethene-based propeller-like dye (TPE). The supramolecules exhibited a nematic LC nature and the different structure of the fluorescent units showed different effect on the LC behaviour of the supramolecules. After being spin-coated onto an oriented PVA film, the liquid crystalline supramolecule film was thermally annealed and the anisotropic fluorescence emission was investigated. A different thermal amplification effect was found depending on the different structure of the fluorescent unit. This conclusion provides a new perspective on the design of a high-performance fluorescence polarization film.