NMR signals can be substantially enhanced using paramagnetic molecules. Microwave excitation of the unpaired electron spin of the paramagnetic molecules transfers the much higher electron spin polarization to the nuclear spins, which is called dynamic nuclear polarization (DNP). Different strategies have been explored, depending on sample conditions (solid or liquid phase, radical concentration, target nuclear spin), and have been theoretically described as Overhauser, solid, cross effect, and thermal mixing. Under favorable conditions these methods may yield an enhancement as large as the ratio of the magnetic moment of the electron and the nuclear spin (e.g., 660 for proton spins). Until recently these methods were explored at low magnetic fields (below 2 T) and for small target molecules. Recent work demonstrated that DNP also gives rise to large signal enhancements at high magnetic fields in the solid as well as in the liquid phase. Applications of DNP at high magnetic fields to biomolecular research and other areas suffering from weak NMR signal intensities are currently emerging. Here, the existing theoretical models regarding DNP are summarized and protocols for up‐to‐date high‐field DNP methods are given, together with a short discussion of their advantages and currently existing limitations.