High‐resolution photothermal ionization spectroscopy has been performed onn‐type high‐purity silicon crystals. Two new shallow donors with binding energies of 36.61 and 36.97 meV, respectively, are observed for the first time, in addition to lithium (Li), lithium‐oxygen complex [D(Li,O)], phosphorus (P), and arsenic (As) donors. These new shallow donors show similar spectral features to Li,D(Li,O), P, and As, which implies that they are also hydrogenic shallow donors. These new complex centers are probably generated during crystal growth. In addition, previously unresolved transitions related to very high excited states of phosphorus as well as the above‐mentioned new shallow donors, have also been observed.