Electronic structures of possible centres of luminescence in the perfect lead (PbWO4) and cadmium tungstate (CdWO4) crystals are calculated using cluster approach. Electronic states of Pb2+, and Cd2+ cations, WO42- and WO66- are obtained on the basis of partial densities of electronic states calculated for several clusters containing from 72 to 104 atoms of the crystals. Calculated energies of one-electron transitions in these centers are compared with experimental data on luminescence and luminescence excitation. Obtained results evidence in favor of a tungstate nature of intrinsic luminescence in the PbWO4 and CdWO4 crystals . I ntrinsic luminescence probably originates from the tungstate groups WO42- in scheelite-type, and from the WO66- groups in the raspite-type PbWO4 crystals. Tungstate groups WO66- are assumed to be the centres of excitation of blue–green and yellow luminescence bands in CdWO4 crystals.