The process of radiative pion capture has in recent years been shown to be a good probe of nuclear structure. The experiments and theoretical results which support this statement are reviewed. High-re solution data on the photon spectra from nuclei ranging in mass l£A<209 are shown. We discuss the observation of giant resonances in T z = +1 nuclei, the quasi-free capture process, and transitions to individual bound nu clear states. The observed transition rates in lp-shell nuclei are compared with recent shell model calculations based on an impulse-approximation Hamiltonian whose ampli tudes are not adjustable constants, but are obtained from the fundamental process on the nucleon, IT" + p -* n + y. The agreement is good within the limits set by the uncertainties of pionic x-ray data. Some features of radiative TT capture on very light nuclei-A=2, 3 and 4-are reviewed. Finally, we discuss the ir" + Li (l"'")-»'Y+°He(0 \) transition where the PCAC hypothesis and soft-pion limit have been applied. The ls-state radiative cap ture rate evaluated with these assumptions is found to agree with impulae approximation calculations and is within reasonable agreement with the recent data when corrections for 2p capture are made.