The invention provides a composite metal oxide catalyst which is a Mo-V-(Te or Sb)-Nb-O composite metal oxide doped with ZrO2, wherein the molar ratio of Zr to Mo is 0.00001-0.01:1. The composite metal oxide catalyst can increase the selectivity of oxidizing propane to synthesize acrylic acid under certain reaction conditions to more than 85% while the yield can reach 45%. The invention also provides a preparation method of the catalyst and an application of the catalyst of oxidizing the propane to synthesize the acrylic acid.