Functionalized hyper-cross-linked polymers with a unique porosity were promising materials, while their facile fabrication remains a challenge. Herein, a novel synthetic strategy was developed based on two Friedel-Crafts alkylation reactions for chloromethylated polystyrene and the hyper-cross-linked phenolic hydroxyl polymers were successfully fabricated. The first lowtemperature reaction (at 313 K) offered the polymers plentiful phenolic hydroxyl and the second high-temperature reaction (at 358 K) provided the polymers with the hyper-cross-linking frameworks with a unique hierarchical porosity. Benefiting from the synthetic protocol, the resultant samples exhibited promising properties for aniline adsorption (q(max): 198.8 mg/g) and CO2 capture (105 mg.g(-1) at 273 K and 1 bar). Moreover, the hierarchical porosity facilitated the kinetic adsorption and about 90 min was enough to reach the equilibrium.