[en] Graphical abstract: BICOTIVOX formulated as Bi₂V_0.9Co_0.1−xTi_xO_5.35+x has been synthesized and the complex impedance has been also illustrated in the Nyquist representation. Highlights: • BICOTIVOX formulated as Bi₂V_0.9Co_0.1−xTi_xO_5.35+x has been synthesized. • γ-BICOTIVOX is stabilized in the all investigated compositions. • The AC impedance spectroscopy for Bi₂V_0.9 Co_0.1−xTi_xO_5.35+x system was also studied in this report. • The total ionic conductivity and dielectric permittivity of BICOTIVOX have been also illustrated. -- Abstract: In the present work Bi₂V_0.9Co_0.1−xTi_xO_5.35+X; 0.02 ⩽ x ⩽ 0.08 was synthesized through standard solid state reaction method. X-ray diffraction and differential thermal analysis has been observed for various compositions and it was found that the tetragonal γ-phase stabilized with γ′ ↔ γ phase transition for all the compositions. The ionic conductivity and dielectric permittivity of BICOTIVOX have been investigated by using AC impedance spectroscopy. The values of two components of complex impedance and the relaxation time of oxide ion movement through the grain interior and grain boundary decrease with increase temperature. The thermal dependence of total ionic conductivity revealed maximum (2.64 × 10⁻⁴ S cm⁻¹) for x = 0.04 at 300 °C