Ce1-xCuxO2 oxide solid solution catalysts with different Ce/Cu mole ratios were synthesized by the one-pot complex method. The prepared Ce1-xCuxO2 catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and H2 temperature-programmed reduction (H2-TPR). Their catalytic properties were also investigated by catalytic combustion of phenyl volatile organic compounds (PVOCs: benzene, toluene, xylene, and ethylbenzene) in air. XRD analysis confirmed that the CuO species can fully dissolve into the CeO2 lattice to form CeCu oxide solid solutions. XPS and H2-TPR results indicated that the prepared Ce1-xCuxO2 catalysts contain abundant reactive oxygen species and superior reducibility. Furthermore, the physicochemical properties of the prepared Ce1-xCuxO2 catalysts are affected by the Ce/Cu mole ratio. The CeCu3 catalyst with Ce/Cu mole ratio of 3.0 contains abundant reactive oxygen species and exhibits superior catalytic combustion activity of PVOCs. Moreover, the ignitability of PVOCs is also affected by the respective physicochemical properties. The catalytic combustion conversions of ethylbenzene, xylene, toluene, and benzene are 99%, 98.9%, 94.3%, and 62.8% at 205, 220, 225, and 225 °C, respectively.