The last decade has witnessed great progress in conjugated polymers for application in optoelectronics. The biggest driving force for the field is to develop polymers with suitable HOMO and LUMO orbital energies, as well as high charge carrier mobility for improved performance in practical devices. Apart from the conventional donor–acceptor (D–A) strategy to tune the optoelectronic properties, the incorporation of main-group elements represents a promising new way to achieve a similar function, however, more efficiently, due to the intrinsic electronic properties of the main-group components. This review highlights the recent advances in main-group element-based conjugated polymers for application in optoelectronics, representatively focusing on Se-, Te-, P-, Si-, Ge-, and B-containing materials.