Lithium Air (Li/O2) batteries are energy conversion devices that produce electricity from the oxidation of lithium metal at the anode and the reduction of molecular oxygen at the cathode. These batteries are considered as promising rechargeable cells for high power applications due to their high power density ranging from 1000 to 2000 Wh/kg. However, one of the most significant challenges is the need to separate the metallic lithium anode from any oxygen or water-containing environment while at the same time allowing fast and efficient lithium ion transport through the electrolyte. Therefore, lithium ion conducting materials that are water and CO2 resistant are a prerequisite. Common materials used as anode protective films and/or Li+ conducting electrolytes for lithium air batteries are perovskite-type oxides (formula: ABO3). Perovskites are good candidates for this application because of their versatility, particularly in regards to ionic conductivity. In the present work, a low cost perovskite family such as SFO (SmFeO3) is developed as a lithium ion conducting material by the introduction of Li+ into its lattice. The perovskites have been synthesized using a solid-state reaction method (SSR) and characterized using different techniques such as powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), energy dispersive X-ray Spectroscopy (EDS) and electrochemical impedance spectroscopy (EIS). The synthesized perovskites are based on samarium lithium ferrite and divided into two groups depending on the formal presence of vacancies in the stoichiometric formula. The first group (SLFO) with no formal vacancies has the stoichiometric formula of SmxLi1-xFeO2+x (where x = 0.1, 0.2, 0.3, 0.5 and 0.7). While the second group (SLFO*) was generated with less metal atoms than specified in the perovskite structure, thereby generating a structure with intrinsic vacancies and with the formula, Sm(x)Li([1-x] – [0.1] or [0.2]) FeO3-δ (where x = 0.3, 0.4, 0.5 and 0.6). Finally, the effect of varying Li and Sm concentrations in both groups and vacancies created in the lattice for the second group, on the ionic conductivity is explored.