High-resolution solid-state NMR spectra can be obtained of cross-linked and high molecular weight polymeric materials by using a combination of magic-angle spinning and high temperature. The resolution of the spectra can be comparable to that seen in solution NMR spectroscopy. This enables standard solution 2D NMR pulse sequences, such as COSY, TOCSY, and HMQC, to be used to assign resonances in these systems. It has been found that short duration pulse sequences work better than long sequences. For observing heteronuclear correlations, carbon-detected 2D pulse sequences appear to have less stringent instrumental setup requirements than proton-detected 2D sequences.