Catalytic conversion of CO2 to methanol has attracted increasing interests as a promising strategy forreducing excessive CO2 emissions. However, the methanol selectivity drops rapidly with elevatedtemperature 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 byadding extra metal, i.e., Al, Cr, Fe or Mg. As-prepared SSCs were characterized and tested in reaction. Theresults 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 theoptimal 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 catalyticperformance. Specifically, the 3Mg-C-ZZ SSC, at 3.0 MPa and GHSV of~2000 h 1, maintains a considerablemethanol selectivity of 81.5 % even at 320 C. Prepared catalysts present remarkable superiorities toconventional copper-based catalysts especially at high reaction temperatures, which endures thempromising applications in coupling conversion of CO2 to valuable chemicals with the intermedia ofmethanol.