The heterogeneous antioxidant, namely, PS-2, 6-DTBP, was easily synthesized from chloromethylated polystyrene (CMPS) with 2, 6-di-tert-butylphenol by a simple one-step Friedel–Crafts reaction. As compared with CMPS (78 m²/g and 34.8 nm, respectively), the Brunauer–Emmett–Teller (BET) surface area (S_BET) of PS-2, 6-DTBP was greatly increased to 623 m²/g, while the average pore size was sharply reduced to 7.0 nm. The antioxidative property of PS-2, 6-DTBP was extensively evaluated by the scavenging activity of superoxide and 2, 2-diphenyl-1-picrylhydrazyl radical (DPPH·) in inhibiting oxidation of benzaldehyde, and the results indicated that 2,6-di-tert-butylphenol loaded on PS-2, 6-DTBP had excellent capability in scavenging O₂⁻· and DPPH·, and effectively inhibited the oxidation of benzaldehyde. As a heterogeneous antioxidant with free radical scavenger, PS-2, 6-DTBP can be conveniently separated from the liquid phase and is environment friendly, showing promising potential in solid antioxidant field.