The lack of signal often limits NMR analysis. Since the signal-to-noise ratio increases with the square root of time, extending the measurement time is not always applicable. An alternative approach is the transient induction of non-Boltzmann spin distribution. This strategy, also called “hyperpolarization”, leads to a dramatic enhancement of the NMR signals. Several different methods are presently explored and applied. Here we present the opportunities for structural biology opened by (photo-)chemically induced dynamic nuclear polarization (photo-CIDNP), i.e., nuclear hyperpolarization occurring in (photo-)chemical reactions involving radical pairs.