Copper valence and environment in two sodium aluminophosphate glasses suggested for immobilization of HLW from reprocessing of spent fuel of uranium-graphite channel reactor (Russian AMB) were studied by XRD, SEM/EDX, XAFS and EPR. Target glass formulations contained ∼2.4-2.5 mol.% CuO. The quenched samples were predominantly amorphous. The annealed MgO free sample had higher degree of crystallinity than the annealed MgO-bearing sample but both them contained orthophosphate phases. Cu in the materials was partitioned in favor of the vitreous phase. In all the samples copper is present as major Cu2+ and minor Cu+ ions. Cu2+ ions form planar square complexes (CN=4) with a Cu2+-O distance of 1.93-1.95 Å. Two more ions are positioned at a distance of 2.76-2.86 Å from Cu2+ ions. So the Cu2+ environment looks like a strongly elongated octahedron as it also follows from the absence of the pre-edge peak due to 1s→3d transition in Cu K edge XANES spectra of the materials. Cu+ ions form two collinear bonds at Cu+-O distances of 1.80-1.85 Å. Thus average Cu coordination number (CN) in the first shell was found to be 2.7-3.0.