Incorporating sulfur (S) atoms into polymer main chains endows these materials with many attractive features, including a high refractive index, mechanical properties, electrochemical properties, and adhesive ability to heavy metal ions. The copolymerization involving S-containing monomers constitutes a facile method for effectively constructing S-containing polymers with diverse structures, readily tunable sequences, and topological structures. In this review, we describe the recent advances in the synthesis of S-containing polymers via copolymerization or multicomponent polymerization techniques concerning a variety of S-containing monomers, such as dithiols, carbon disulfide, carbonyl sulfide, cyclic thioanhydrides, episulfides and elemental sulfur (S8). Particularly, significant focus is paid to precise control of the main-chain sequence, stereochemistry, and topological structure for achieving high-value applications.