Two series of silsesquioxanes-based porous polymers have been synthesized via Friedel-Crafts reaction of octavinylsilsesquioxane with tetrabiphenylsilane and octabiphenylsilsesquioxane as building blocks. The synthesized hybrid porous polymers possess specific surface areas up to 1500 m(2) g(-1), pore size distributions with uniform micropores centered at 1.4 nm and mesopores centered at approximate to 4.0 nm, large pore volumes up to 1.30 cm(3) g(-1), high fluorescence intensities and good thermal stabilities. More importantly, the porosities and fluorescence emissions of these porous polymers can be tuned systematically by adjusting the geometry of node and molar ratio of reactants. They exhibit a high adsorption ability of bulky dyes (i.e., rhodamine B, Congo red, crystal violet) and heavy metal ions. For example, the equilibrium adsorption capacity for Congo red and Pb2+ achieves as high as 2230 mg g(-1) and 300 mg g(-1), respectively. These results suggest that these porous polymers may have potential applications in water purification.