Abstract Lanthanum orthoantimonate was synthesized using a solid‐state synthesis method. To enhance the possible protonic conductivity, samples with the addition of 1 mol % Ca in La‐site were also prepared. The structure was studied by the means of X‐ray diffraction, which showed that both specimens were single phase. The materials crystallized in the space group P 2 1 / n . Dilatometry revealed that the material expanded non‐linearly with the temperature. The nature of this deviation is unknown; however, the calculated linear fraction thermal expansion coefficient was 9.56×10 −6 K −1 . Electrical properties studies showed that the material is a proton conductor in oxidizing conditions, which was confirmed both by temperature studies in wet in dry air, but also by the H/D isotope exchange experiment. The conductivity was rather modest, peaking at the order of 10 −6 S cm −1 at 800 °C, but this could be further improved by microstructure and doping optimization. This is the first time protonic conductivity in lanthanum orthoantimonates is reported.