YVO₄:Er³⁺, Yb³⁺ with varying Yb³⁺ concentrations were prepared by a precipitation method. The results of X-ray diffraction (XRD) show that all the samples have a tetragonal zircon structure; the calculated average crystallite sizes are in the range of 14–22 nm. The lattice constants and cell volume of the samples decrease slightly with the increase in Yb³⁺ concentration. The upconversion luminescence spectra of all the samples were studied under 980 nm laser excitation. The strong green emission is observed, which is attributed to the ²H_11/2 → ⁴I_15/2 and ⁴S_3/2→⁴I_15/2 transitions of Er³⁺, and the red emission peaks in 650–675 nm can be ignored. The emission intensity for the sample depends on the Yb³⁺ concentration. These results reveal that the upconversion processes of YVO₄:Er³⁺, Yb³⁺ are related to the structure and the doping Yb³⁺ concentration of the sample.