(Ba0.92-xCa0.08Ndx)(Ti0.82Zr0.18)O3 (0≤x≤0.02) Ferroelectric ceramics samples were prepared by conventional solid-state reaction methods. The structure and dielectric properties of the samples were investigated by XRD, LCR and other techniques. The results revealed that when the doping amount is 0.015, the second phase occurred. The structure of defects, charge compensation and configuration of [4NdBa.+VTi’’’’] defect cluster were discussed in BCZT ceramics doped with Nd3+ using the general utility lattice program (GULP). With Nd3+ content increasing, both dielectric constant and dielectric loss declined, the dielectric peak temperature shifted to low temperature and the dielectric peak broadened. With increasing Nd3+ content, the dielectric relaxation characteristics were obtained, which were attributed to the random field induced by off-center Nd3+ ions and defect dipoles [4NdBa.+VTi’’’’].