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Data presented in this article are related to the research article entitled O2−–V5+ charge transfer band, chemical bond parameters and R/O of Eu3+ doped Ca(VO3)2 and Ca3(VO4)2: A comparable study[ing Li, Yu Pan, Wenjun Wang, Zihao Wen, Xuanxi Leng, Qi Wang, Liqun Zhou, Haibing Xu, Qinghua Xia, Li Liu, Hongping Xian, Xiaoguang Liu]. The data present the fitting results of the broad excitation spectra of Ca(VO3)2:1%Eu and Ca3(VO4)2:1%Eu using the Gaussian model, the O/R values using the experimental PL emission results. The data compares the optimized cell parameters for Ca(VO3)2: 1%Eu and Ca3(VO4)2:1%Eu through the CASTEP geometry optimization with their initial cell parameters.