In this paper, a new series of luminescence liquid crystalline polymers with rare earth Eu(Ⅲ) complexes were reported for the first time. Such complexes were prepared by grafting copolymerization of the chiral liquid crystalline monomer (M1), 4-allyloxylbenzoic acid cholesteryl and complexes (C3) of Eu(Ⅲ) onto hydrosiloxane. The relationship between the conjugation effect of Eu3+ and luminescence properties was investigated here. Under stimulation by UV light, high luminescence intensity of such complexes was observed at ambient temperature with λmax at 617nm. When the content of Eu(Ⅲ) is under 8%, luminescence intensity increases with the increasing of Eu(Ⅲ) content. Such trend reverses once the content is above 10%.Advantage of such complex was demonstrated by the difference of the luminescence intensity of the complex of polymer and the complex of polymermonomer C3, which is only 30% of the former. Compared with polymer without Eu(Ⅲ), the LC texture remained the same, with higher Tm and lower TC. Besides superior luminescence properties, such Eu(Ⅲ) complex also had excellent processibility due to innate liquid crystal nature. The theoretical study of Eu(Ⅲ) liquid crystal complex can provide foundations to potentially wide industrial application.