The effect of Molybdenum (Mo) doping in pure barium titanate at Ti site has been investigated using electron microscopy, x-ray diffraction and dielectric and impedance spectroscopy. The room temperature XRD data confirms the formation of Mo substituted BaTi 0.94 Mo 0.06 O 3 in tetragonal symmetry. Even with the minimal doping of Mo, the first two structural transition shifts to the lower temperature by 60 and 30 K, respectively, as compared to pure barium titanate, confirmed via dielectric, polarization and x-ray diffraction measurements. In Mo doped BaTiO3 , 3 , the cubic to tetragonal phase transition has been observed at 335 K, tetragonal to orthorhombic at 250 K. The orthorhombic to rhombohedral transition remains almost unaffected with Mo doping. Furthermore, transmission electron microscopy (TEM) has been employed to see the changes in microstructure/ domain structure across various ferroelectric phases below 335 K which confirms the emergence of multiple twins in different ferroelectric phases.