In this work, EuF 3 and NaYF 4 nanocrystals were prepared by liquid-solution-solid (LSS) method respectively, high-resolution transmission electron microscopy (HRTEM) images revealed that the as-prepared NaYF 4 nanocrystals were monodisperse nanoparticles with the size about 30 nm; while the as-prepared EuF 3 were polydisperse nanoparticles with the size of 5~20 nm. And they were used to prepare a series of novel ternary complex hydrogels of EuF 3 -NaYF 4 nanocrystals/poly(N-isopropyl acrylamide) (PNIPAm) by free radical polymerization. In a typical synthesis, 2 mg the as-prepared EuF 3 and NaYF 4 nanocrystals, 201.6 mg reactants of N-isopropyl acrylamide (NIPAm), N,N'-methylenebisacrylamide (BIS) and azodiisobutyronitrile (AIBN) (m NIPAm ∶m BIS ∶m AIBN =200/0.2/1.4) and 4 mL CHCl 3 were mixed and added into a 10 mL sealing tube. The tube was placed into an ultrasonic oscillator for about 10 min to obtain a uniform mixture, and then oxygen was removed by bubbling N 2 and successfully exerting vacuum on the tube for about 5 min. After the operation was repeated three times, the tube was sealed and kept at 60 ℃ for 3 h. After that, the crude complex hydrogels were synthesized. Finally, the crude hydrogels were immersed into deionized water to remove the remained monomers and impurities. The total time of soaking was about 7 d, and the deionized water was replaced every 10 h. Following the above procedure, all of the mentioned EuF 3 -NaYF 4 /PNIPAm complex hydrogels were obtained. The structure and fluorescent properties of the complex hydrogels were investigated by differential scanning calorimeter (DSC), photoluminescence (PL), Fourier transform infrared (FTIR), X-ray diffraction (XRD). And the thermosensitive fluorescent behavior of the complex hydrogels was investigated and the mechanism was discussed in detail. The results suggested that, in the PNIPAm hydrogel matrix, energy can be transferred between the bulk doped EuF 3 nanocrystals and NaYF 4 nanocrystals. Either the relative content of two kinds of nanocrystals or the ambient temperature plays an important role in the thermosensitive fluorescent behavior of the complex hydrogels.