For the first time the LaIn1-xZnxO3-1/2x samples was synthesized via solid-state reaction method. The Zn2+−doping effect on the B-site of LaInO3 on structure, water uptake and electrical properties was investigated. The results show that Zn2+ is good alternative to alkaline earth metals. The Zn-doping decreases the sintered temperature and makes it possible to obtain high-density ceramics. The substitution increases the conductivity by ∼2 orders of magnitude. Below ∼500 °C the phases exhibit the dominant oxygen-ionic transport (dry atmosphere), and the dominant protonic transport below 600 °C (wet atmosphere). The obtained results suggest the prospects for using these materials in the Hydrogen Energy field. A new concept of the ability of perovskite phases LaBO3 to incorporate water has been proposed. In addition to the presence of oxygen vacancies, their size, which depends on the B-cation nature, is of decisive importance in the hydration process and the formation of proton conductivity. © 2023 Hydrogen Energy Publications LLC.