Ba0.62Sr0.38TiO3 ceramics of perovskite structure are prepared by solid reaction method with the addition of x wt% NiO and their dielectric properties are investigated. It is found that Ni2+ can enter the B site in ABO3 perovskite when doping concentration is less than 0.6 wt%, whereafter, Ni2+ ions most segregates on the grain boundaries to inhabit the grain growth. Due to the decrease of grain size and the impurity, the dielectric constants are decreased. Decrease of dissipation factor is attributed to appearance of the oxygen vacancy and disappearance of the reduction of Ti4+ ion. It is concluded that the diffuse phase transition is linked to the adulteration of Ni2+. The disordering, mechanical stress in the grain and the oxygen vacancies are produced because of the adulteration of Ni2+, and the diffuse phase transition increases with the level of doping increasing, leading to that the peaks of dielectric constants becomes slower and flatter.