Mesoporous Ce0.5Zr0.5O2 solid solution catalyst was synthesized by a sol-gel process using block copolymer Pluronic P123 as the template. The as-prepared catalyst was characterized by X-ray diffraction, H-2-Temperature-programed reduction, BET, and X-ray photoelectron spectra techniques. The catalytic properties of the catalyst were evaluated by the synthesis of iso-C-4 hydrocarbons via CO hydrogenation. The mesoporous catalyst showed much better catalytic selectivity and yield of isobutene and isobutane (i-C-4) from CO hydrogenation at 673-723 K, 5.0 MPa, and 720 h(-1), than the solid Ce0.5Zr0.5O2 catalyst prepared by coprecipitation. This was due to the higher BET surface area, pore volume and the reducibility of the mesoporous Ce0.5Zr0.5O2 catalyst.