The performance of semiconducting polymers has been steadily increasing in the last 20 years. Improved control over the microstructure of these materials and a deeper understanding of how the microstructure affects charge transport are partially responsible for such trend. The development and widespread use of techniques that allow to characterize the microstructure of semiconducting polymers is therefore instrumental for the advance of these materials. This article is a review of the characterization techniques that provide information used to enhance the understanding of structure/property relationships in semiconducting polymers. In particular, the applications of optical and X-ray spectroscopy, X-ray diffraction, and scanning probe techniques in this context are described.