Lanthanum doped 95BiFeO3–5BaTiO3 (95BLFO–5BT) multiferroic ceramic was prepared under extreme conditions by a PVA Sol-Gel method. A deep study of dielectric properties of La doped 95BiFeO3– 5BaTiO3 (95BFO–5BT) ceramics with the help of comprehensive analysis of temperature and frequency dependent dielectric behavior is reported in this paper. Dielectric properties of 95BLFO–5BT ceramics were studied at various temperature and frequency. It was also found that doping of 95BiFeO3–5BaTiO3 by Lanthanum improved dielectric properties. The dielectric constant of a 95BiFeO3–5BaTiO3 (95BLFO–5BT) increased after Lanthanum doping for both low and high frequency. The dielectric constant was found to be very high (ε′ > 103, for T > 150°C). This enhancement in the dielectric properties is possible due to the changes in structure of as prepared sample of 95BiFeO3– 5BaTiO3 (95BLFO– 5BT) by the addition of Lanthanum.