Bi-substituted Ti–Ni perovskite of different compositions La1-xBixNi0.5Ti0.5O3 were elaborated utilizing the sol–gel method. TGA thermogravimetric and DSC calorimetric analysis was used to obtain the optimal sample formation temperature. XRD Results showing that samples have crystallized in the orthorhombic structure, belonging to the Pnma spatial group. The purity and morphology of nano-grains were investigated by EDX and SEM. Dc conductivity is specified by SPH model at high temperatures and VRH model at low temperatures. The AC conductivity spectra follow to Jonscher’s universal power law. The Ghosh scale law was investigated to understand the ionic dynamics of compounds. The estimated activation energy values from alternative conductivity and impedance verify that relaxation process and electrical conductivity can be associated with the same type of charge carriers. The equivalent electrical circuit was utilized for modeling the Nyquist data. The observed high conductivity values indicate that our samples may be suitable for applications in the electrical devices