We investigated the charge distribution in Pr1+xBa2−xCu3O6+y-crystals at liquid-He temperature by means of 63,65 Cu-and 141 Pr-NMR and NQR. The electric field gradients determined for the different oxygen coordinations of Cu(1) on the chains confirm the model that the hole states are localized in the O2pπ-orbitals of the CuO2-planes. The intensity and line-shape analysis of the Cu(1)-and Pr-resonances in the oxygen doping series (x ≈ 0, y = 0 . . . 1) and in the Pr/Ba solidsolution series (at y = 1) allows us to assign the Pr-resonance to Pr at RE-sites. Therefore, we can investigate the charge distribution in the CuO2-Pr-CuO2-layers by crystal field analysis of the Pr-signal. To consistently describe our results with neutron scattering data we propose that two Pr-states are present in the RE-layer, and ascribe them to Pr with and one without a hole localized in the oxygen coordination shell. NMR detects only the former, with a virtually nonmagnetic singlet ground state, while space-integral techniques are dominated by the latter, due to a quasi-doublet ground state and antiferromagnetism of its Pr-moments at low temperature.