We investigated the doping-site dependence of upconversion (UC) emission characteristics of Ho3+ and Yb3+ ions co-doped BaHfO3 (BHO). The Ho3+ and Yb3+ ions could be doped in Ba-site (A-site) and Hf-site (B-site) of BHO. Under 980-nm near-infrared excitation, we detected sizable green (550 nm) and red (660 and 760 nm) UC emissions from Ho3+ ions assisted by Yb3+ ions. More interestingly, the UC emission intensities of B-site doped samples were greater than those of A-site doped samples. We suggested that the asymmetry ratio in the local structure around Ho3+ ions should be an important factor for the UC emission.