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Several molybdates of nearby composition were found while studying of Ln2O3-MoO3 systems: fluorite-like cubic Ln5Mo3O16 compounds (5:6) with mixed electron-ion conductivity of interstitial type, and Ln2MoO6 oxymolybdates (1:1), which conductivity has been studied insufficiently. The structure of rare-earth Ln2MoO6 (Ln = La, Pr, Nd) oxymolybdates is tetragonal, layered, constructed of two fluorite layers and a layer of isolated tetrahedra. A feature of the cubic structure of fluorite-like compounds Ln5Mo3O16 was the existence of isolated Mo tetrahedra near sufficiently large voids. The purpose of this work was to reveal the effect of doping of oxymolybdates and fluorite-like compounds on their physical properties. It was found that a wide range of (PbO)x(La2MoO6)(1-x)/2 solid solutions with a layered tetragonal structure is formed in the Ln2MoO6–PbO system by lead doping. The range of solid solutions was 0≤x≤0.34 for Ln = La and 0≤x≤0.6 for Ln = Nd. Doping with lead resulted in an unusual effect, the appearance of a superionic reversible phase transition. This transition was observed at 820 °C for compounds with Nd and at 775 °C with La. The existence of this transition was confirmed by DSC and electrophysical measurements. At the temperatures indicated above, a superionic jump in the conductivity by two orders of magnitude and a dielectric anomaly of the ferroelectric type were observed. In oxyfluorides MeLn4Mo3O15F a phase transition of the ferroelectric type with a jump in the electrical conductivity by 2 orders of magnitude also arises in the region of 600-800 °C. It can be assumed that the appearance of a phase transition and a radical change in the electrophysical properties of rare-earth doped oxyfluorides and oxymolybdates may be due to weak structural changes, which are not detected by powder XRD methods.