A SiO2 microsphere imprinted by phosphate ions was prepared with the use of phosphate ion as the template molecule and tetraethoxysilane as the precursor. Thereafter, the imprinted SiO2 microspheres were modified with 3-(trimethoxysilyl)propyl methacrylate (TMSPMA@SiO2), followed by introducing the double bond. In the presence of TMSPMA@SiO2, using N-isopropylacrylamide as monomer, and potassium persulfate as initiator, polymer/inorganic hybrid particles (PNIPAM/SiO2) were prepared. Fourier transform infrared spectroscopy, thermogravimetric analysis, nitrogen adsorption-desorption test, and transmission electron microscope were employed for the characterization of molecular imprinted SiO2 microspheres and PNIPAM/SiO2 hybrid particles. The effects of phosphate concentration, pH value, and adsorption temperature on the phosphate binding properties of PNIPAM/SiO2 hybrid particles were studied by UV-vis spectrophotometer. The experimental results shed light on the fact that the PNIPAM structure is beneficial for the improvement of the adsorption ability of phosphate-imprinted SiO2microspheres. With the increase in the initial phosphate concentration, the adsorption capacity of hybrid particles to phosphate ions increased to 274 mg/g at pH = 7 and 15 °C. The acid condition and the temperature below the low critical solution temperature (LCST) of PNIPAM are favorable to the adsorption of phosphate ions by PNIPAM/SiO2 hybrid particles, and the maximum adsorption capacity can reach 287 mg/g (at pH = 5 and 15 °C). The phosphate imprinted polymer/inorganic hybrid material is expected to be put to use in the fields of phosphate ions adsorption, separation, and recovery.