AbstractTime‐resolved luminescence measurements have been carried out for PbMoO4 crystals with the scheelite structure. A fast‐decaying luminescence band with a lifetime of the order of 10 ns is observed at 400 nm at low temperatures (T < 170 K). This luminescence is tentatively assigned to the radiative transition of a singlet excited state of a self‐trapped exciton (STE) located on a (MoO4)2–ion. The green luminescence, which is ascribed to the triplet STE states in PbMoO4, is found to consist of three emission bands peaking at 405, 520, and 600 nm at T = 150–220 K. Such a composite nature is explained by taking into account the symmetry lowering of (MoO4)2– ions due to the Jahn‐Teller effect. The present observation provides strong support to the previous results of PbWO4, in which the triplet STE luminescence is also decomposed into three individual bands. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)