Catalytic conversion of CO2 to methanol has attracted increasing interests as a promising strategy for reducing excessive CO2 emissions. However, the methanol selectivity drops rapidly with elevated temperature due to enhanced CO synthesis using conventional catalysts, which hiders its application. Herein, ZnO-ZrO2 solid solution catalysts (SSCs) were prepared with different methods and modified by adding extra metal, i.e., Al, Cr, Fe or Mg. As-prepared SSCs were characterized and tested in reaction. The results show that prepared ZnO-ZrO2 SSCs possess similar chemical compositions but different crystals, morphologies and pore systems, among which the C-ZZ synthesized by co-precipitation exhibits the optimal property. After doping, the basic crystal of tetragonal ZrO2 can be retained and ternary ZnO-ZrO2-MOx SSCs are successfully prepared. There come dramatic improvements in overall catalytic performance. Specifically, the 3Mg-C-ZZ SSC, at 3.0 MPa and GHSV of~2000 h-1, maintains a considerable methanol selectivity of 81.5 % even at 320 C. Prepared catalysts present remarkable superiorities to conventional copper-based catalysts especially at high reaction temperatures, which endures them promising applications in coupling conversion of CO2 to valuable chemicals with the intermedia of methanol.