A new quaternary phosphonium modified hierarchically macro/mesoporous silica (named HPS-P) was prepared by a sol-gel method accompanied by phase separation by using PEG-10000 as surfactant and tetramethoxysilane as silicon source, followed by reacting with quaternary phosphonium. The resultant HPS-P containing large macroporous skeleton with an average diameter of 0.67 mu m and mesopores with an average diameter of 10.3 nm has a specific area of ca. 254.7 m(2) g(-1). The adsorption of HPS-P for ReO4- was investigated, and the adsorption equilibrium could be achieved within 1 min; the adsorption isotherm data for ReO4- could be well fitted with a modified Langmuir model. Moreover, HPS-P has excellent adsorption selectivities toward ReO4- with competing anions, including NO3-, SO42-, and Cl-. The Delta H-Theta and Delta S-Theta of the Cl-/ReO4- ion-exchange reaction of HPS-P were calculated to be -4.5 kJ mol(-1) and 12.6 J mol(-1) K-1, respectively, indicating that the adsorption of ReO4- onto HPS-P is a spontaneous physical adsorption process. In dynamic column experiment, HPS-P could be recycled by 2.2 mol L-1 HNO3 with a good performance within 3 min. IR and XPS analysis confirmed that the adsorption mechanism is ion-exchange.