Defect structures of Eu3+-doped PbWO4 crystals are investigated by site-selective laser-excitation spectroscopy. The excitation spectrum of the F-7(0) -> D-5(0) transition shows a strong dependence on Eu3+-concentration in PbWO4 crystals. Only one substitution site for Eu3+ is identified in the PbWO4:Eu3+ (0.01 at.%) crystal. while at least six inequivalent sites are observed in the PbWO4:Eu3+ (0.05 and 0.5 at.%) crystals. The charge compensation mechanisms for the observed sites are discussed in relation with annealing effects and temperature-dependent decay curves. The dominant site for Eu3+ in the PbWO4 lattice seems to be due to a formation of Eu-pb(3+) - V-Pb '' dipole by charge compensation. The minor sites for Eu3+ are attributable to the Eu-pb(3+)-O-i '' dipole, a site perturbed by Eu-pb(3+center dot)-V-Pb '' dipole, and a clustering of Eu3+ in the PbWO4 lattice. The energy transfer and site distribution of Eu3+ are discussed in PbWO4:Eu3+ are discussed in PbWO4:Eu3+ (0.01, 0.05, and 0.5 at.%).