In the system PbF2–NdF3–SnF2 are formed solid solutions of the heterovalent substitution Pb0,86-хNdхSn1,14F4+х (0 < x ≤ 0,17) with structure of β–PbSnF4. At x > 0,17 on the X-ray diffractograms, in addition to the basic structure, additional peaks are recorded to the reflexes of the individual NdF3. For single-phase solid solutions, the calculated parameters of the crystal lattice are satisfactorily described by the Vegard rule. The introduction of ions of Nd3+ into the initial structure leads to an increase in the parameter с of the elementary cell from 51.267 Å for x = 0,03 to 51.577 Å for x = 0.17. The replacement of a part of leads ions to neodymium ions an increase in electrical conductivity compared with Pb0.86Sn1.14F4. The slight replacement (3.0 mol. %) of Pb2+ ions by Nd3+ in the structure of Pb0.86Sn1.14F4 causes an increase in the electrical conductivity at T> 530 K (6.88·10-2 S/cm compared to 2.41·10-2 S/cm for the initial sample compound Pb0.86Sn1.14F4). In the region of lower temperatures, the electrical conductivity of the samples of this composition decreases, and below that temperature, on the contrary, slightly reduces the electrical conductivity, approaching the values characteristic of β-PbSnF4. The activation energy of the conductivity thus increases over the entire temperature range. A further increase in the concentration of Nd3+ ions in the synthesized samples causes an increase in their fluoride-ion conductivity throughout the temperature range. It should be noted that samples with a content of 10-15 mol% NdF3 at T>500 K have comparable conductivity values. At lower temperatures, the higher the conductivity, the higher the concentration of the substituent. The highest conductivity and the lowest activation energy have the sample Pb0.69Nd0.17Sn1.14F4.17 (σ373=3.68·10-2 S/сm, Ea=0,1 eV). The fluorine anions in synthesized phases are in three structurally-equivalent positions. The charge transfer is provided by the highly mobile interstitial fluorine anions, whose concentration increases with increasing temperature and concentration of NdF3. The transfer numbers for fluorine anions are not less than 0.99, practically independent of the concentration of neodymium trifluoride.