The present work is devoted to the theoretical interpretation of nuclear magnetic resonance (NMR) spectra on nonmagnetic lanthanum ion in charge-ordered La0.5Ca0.5MnO3 and La0.33Ca0.67MnO3 compounds. It is shown that the anisotropic hyperfine interaction, which arises due to the polarization of lanthanum’s external p-shells, plays a crucial role in spectrum forming. Our model allows to explain experimental spectra. The work is partially supported by CRDF REC-005.