[en] The Pr_0.79Na_0.21MnO₃ perovskite has been prepared in polycrystalline form by a ceramic method. We have carried out its structural characterization by synchrotron X-ray powder diffraction (SXRPD) at room temperature and at 150 K (T< T_CO). In the charge ordering (CO) state, the SXRPD data can be refined both on the basis of the site-centred model and the bond-centred model proposed for half-doped manganites, without a clear advantage of one model over the other. From the dielectric point of view, at the CO temperature this manganite shows a maximum in the dielectric constant whose origin is intrinsic, and cannot be attributed to the presence of extrinsic factors. We relate this dielectric behaviour to the formation of polar entities at the temperature of charge condensation, due to an asymmetric charge distribution intermediate between site-centred and bond-centred type. - Graphical abstract: We have prepared the near half-doped Pr_0.79Na_0.21MnO₃ perovskite, whose SXRPD data can be refined both on the basis of the site-centred and bond-centred model in the CO state. Its dielectric constant shows an anomaly at T_CO whose origin is intrinsic and that we relate to the formation of polar entities at the temperature of charge condensation due to an asymmetric intermediate charge distribution. Display Omitted