Polymer semiconductors have been experiencing a remarkable improvement in electronic and optoelectronic properties, which are largely related to the recent development of a vast library of high-performance, donor–acceptor copolymers showing alternation of chemical moieties with different electronic affinities along their backbones. Such steady improvement is making conjugated polymers even more appealing for large-area and flexible electronic applications, from distributed and portable electronics to healthcare devices, where cost-effective manufacturing, light weight, and ease of integration represent key benefits. Recently, a strong boost to charge carrier mobility in polymer-based field-effect transistors, consistently achieving the range from 1.0 to 10 cm2 V−1 s−1 for both holes and electrons, has been given by uniaxial backbone alignment of polymers in thin films, inducing strong transport anisotropy and favoring enhanced transport properties along the alignment direction. Herein, an overview on this topic is provided with a focus on the processing–structure–property relationships that enable the controlled and uniform alignment of polymer films over large areas with scalable processes. The key aspects are specific molecular structures, such as planarized backbones with a reduced degree of conformational disorder, solution formulation with controlled aggregation, and deposition techniques inducing suitable directional flow.