The LaB6-SiO2-Canadian resin sols with different doping content of LaB6 were prepared by using the lanthanum hexaboride(LaB6) nanomaterials, Canadian resin sol and nano-SiO2, and then coated on the surface of plastic optical fiber to form a photoluminescence heating and spectral beam splitting utilizing optical fiber. The absorption spectrum and heating rate of LaB6 particles were tested, and the effects of the doping content of LaB6 and the thickness of the coating layer on the luminous heating performance of the fiber surface were investigated. The results showed that the LaB6 exhibited weak absorption at the wavelength of 510~650 nm for light radiation, while exhibited strong absorption for light at other visible-near infrared bands for heat generation. When the mass fraction of LaB6 is 0.30% and the coating thickness is 200 μm, the uniformity of photoluminescence heating on the surface of optical fiber is the best, and the average luminous intensity and average heating rate of the observation points reach 26.59 μW/cm2 and 0.29 ℃/min, respectively, and realizes the utilizing of spectral beam splitting in the visible-near infrared spectrum.