A concise and facile one-pot sol-gel method was proposed by using 3-aminophenol/formaldehyde (AF) resin as soft template, tetraethyl orthosilicate (TEOS) as silicon source, hexadecyl trimethyl ammonium bromide (CTAB) as pore-forming agent for synthesizing silica microparticles. In the synthesis process, modification of soft template 3-aminophenol/formaldehyde (AF) resin structure and hydrolysis rate of TEOS was made by simply changing reaction temperature, a series of SiO₂ microspheres with different structures and morphology could be obtained. The microstructure and characteristic of the SiO₂ microparticles were characterized by means of scanning electron microscope (SEM), transmission electron microscopy (TEM), N₂ adsorption-desorption specific surface areaanalysis (BET) and Fourier transform infrared spectroscopy (FTIR). The results show that as the reaction temperature increases from 0℃^{to 100℃, SiO₂ microparticles presented various type of structures such as solid sphere, yolk-shelled sphere, single-shelled sphere, and broken solid sphere. The HMS microspheres with hollow yolk-shelled morphology possessed a large specific surface area (513 m2/g), large pore volume (0.432 cm3/g), and uniform mesopores (3.66 nm). In addition, the yolk-shelled HMS was subjected to acrylonitrile free radical polymerization, amidoxime treatment to obtain HMS-grafted-polyamidoxime (HMS-g-PAO), which were used in the adsorption test of CrVI in K₂Cr₂O₇ solution at pH=2. The modified HMS microspheres had an excellent adsorption ability to CrVI in K₂Cr₂O₇ solution, and the adsorption amount could reach 140 mg/g when adsorption balanced.}