Two novel hybrid porous polymers were easily prepared by the Friedel-Crafts reaction of octavinylsilsesquioxane with triphenylphosphine and triphenylphosphine oxide, respectively. They possessed unique bimodal pores with uniform micropores and mesopores centered at 1.5 nm and 3.7 nm, respectively, high surface areas up to 1105 m 2 g À1 , high thermal stability and an excellent sizeselective adsorption for dyes. These hybrid porous polymers are very promising in dye separation, water purification and treatment.