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Substituting Cd2+ions into the A and B sites in a Pb(Ni1/3Nb2/3)O3PbZrO3PbTiO3(PNNPZPT) ternary perovskite material made it possible to determine the effects of the Cd2+ion substitution site on sintering behavior. The substitution site of the Cd2+ion was identified by using X‐ray photoelectron spectroscopy spectra. Although Cd2+ions were substituted into the A and B sites in PNNPZPT, the Cd2+ions preferred the A site over the B site. When Cd2+ions replaced Pb2+ions, a weight gain was observed during sintering. On the other hand, replacing Ni2 ions with Cd2+ions promoted weight loss. Those weight changes indicated that Cd2+ions change the bonding strength between the B‐site cations and the oxygen of the octahedron in a perovskite structure. Density was influenced by the Cd2+ion substitution site, and the A‐site‐doped compositions had higher densities than the B‐site‐doped compositions.