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The luminescent properties of CdWO4:Tb,Li crystals have been investigated at 10 K in the region 4-25 eV using synchrotron excitation. It is shown that besides the intrinsic matrix luminescence the number emission lines due to electron f-f-transitions in Tb3+ ions are eficiently excited at near-edge region of the fundamental absorption (Eexc = 4:1 eV). The weak recombination luminescence of terbium impurity on the background of intensive matrix luminescence is observed under excitation in the region of fundamental absorption (Eexc = 5:4 and 13.8 eV). It is shown that the luminescence spectrum of the matrix is a superposition of three elementary bands 2.07, 2.47, and 2.73 eV. The nature of emission bands is discussed. [ABSTRACT FROM AUTHOR]