Sulfur is a massive byproduct of the petrochemicals industry and hardly employed as a building block for porous organic polymers (POPs). Here, a new family of sulfur-bridged POPs has been prepared via a C–H insertion reaction between sulfur and polycyclic aromatic hydrocarbons. Sulfur works as a solvent, external cross-linker, and porogen simultaneously during the polymerization process. The products demonstrate high porosity and maximum surface area of 1050 m2 g–1 with abundant accessible active sites, contributing to the nanometerization of sulfur and significantly enhancing the inherent affinity between heteroatoms toward soft metal ions. Therefore, they exhibit a high absorption capacity for Au(III) of 3287 mg g–1 and excellent absorption selectivity and removal efficiency via a performance evaluation even in real electronic wastewater. This synthetic strategy to prepare high added-value functional POPs with sulfur not only sheds light on designing high-performance gold adsorption materials and emerging POPs, but also promotes a sustainable development protocol.