Solid-state NMR with dynamic nuclear polarization (DNP-NMR) has recently attracted attention as a highly sensitive NMR measurement method for analyzing polymers. We recently investigated DNP-NMR for insoluble polymers, particularly cross-linked polymers, engineering plastics, and polymer-supported catalysts, and achieved high NMR signal sensitivity at a routinely accessible level. In this focus review, we present case studies on DNP-NMR measurements for a wide range of polymers.