Abstract

Recent decades have witnessed the rapid development of semiconducting polymers in terms of high charge mobilities and applications in transistors. Significant efforts have been made to develop various conjugated frameworks and linkers. However, studies are increasingly demonstrating that the side chains of semiconducting polymers can significantly affect interchain packing, thin film crystallinity, and thus semiconducting performance. Ways to modify the side alkyl chains to improve the interchain packing order and charge mobilities for conjugated polymers are first discussed. It is shown that modifying the branching chains by moving the branching points away from the backbones can boost the charge mobilities, which can also be improved through partially replacing branching chains with linear ones. Second, the effects of side chains with heteroatoms and functional groups are discussed. The siloxane‐terminated side chains are utilized to enhance the semiconducting properties. The fluorinated alkyl chains are beneficial for improving both charge mobility and air stability. Incorporating H bonding group side chains can improve thin film crystallinities and boost charge mobilities. Notably, incorporating functional groups (e.g., glycol, tetrathiafulvalene, and thymine) into side chains can improve the selectivity of field‐effect transistor (FET)‐based sensors, while photochromic group containing side chains in conjugated polymers result in photoresponsive semiconductors and optically tunable FETs.