The local structure of an alternative Pb(Zn1/3Nb2/3)O3-based perovskite ceramic is investigated. The 0.07 BaTiO3-0.93 Pb(Zn1/3Nb2/3)O3 ceramic is synthesized using a combination of Zn3 Nb2 O8 B-site precursor and BaTiO3 perovskite phase stabilizer. Then, x-ray absorption spectroscopy and density functional theory are employed to calculate the local structure configuration and formation energy of the prepared samples. Ba2+ is found to replacePb)2+ in A-site with Zn2+ occupying B-site in Pb(2 n1/3Nb2/3)O3, while in the neighboring structure, Ti4+replaces Nb5+ in B-site with Pb2+ occupying A-site. With the substitution of BaTiO3 in Pb(Zn1/3Nb2/3)O3, the bond length between Zn2+ and Pb2+ is longer than that of the typical perovskite phase of Pb(Zn1/3Nb2/3)O3.This indicates the key role of BaTiO3 in decreasing the steric hindrance of Pb2+ lone pair, and the mutual interactions between Pb2+ lone pair and Zn2+ and the formation energy is seen to decrease. This finding of the formation energy and local structure configuration relationship can further extend a fundamental understanding of the role of BaTiO3 in stabilizing the perovskite phase in PbZn1/3Nb2/3O3-based materials,which in turn will lead to an improved preparation technique for desired electrical properties.