Abstract The luminescence properties of La3WO6Cl3 are reported and discussed. The tungstate group occurs as a trigonal prismatic WO6−6 complex. The blue luminescence is, for the greater part, quenched at room temperature. No energy migration occurs in this lattice. The decay times are discussed in terms of a simple molecular-orbital (MO) scheme. The luminescence of the following activating ions was studied: Mo6+, Bi3+, Eu3+, Sm3+, Ce3+, and Tb3+. The molybdate group produces a red emission with low efficiency. The Bi3+ ion induces a narrow band emission with small Stokes shift. This is interpreted using a Bi3+O2−W6+ charge-transfer state. Except for Ce3+, the rare earth activators show luminescence, but the total transfer efficiency from tungstate to the rare-earth ions is low. This is not due to the one-step tungstate-rare-earth transfer (which is efficient), but to the localized nature of the tungstate excitation. The Eu3+ charge-transfer band is at very low energies.