Disordered macroporous La2O2CO3/ZnO materials were prepared by a solution combustion method, and then their microstructures and La2O2CO3 phases were investigated as functions of La/Zn ratios and calcination temperatures. All of the materials prepared by the solution combustion method clearly showed disordered macroporous morphology whose framework was composed of ZnO and La2O2CO3 nanoparticles. A monoclinic La2O2CO3 structure was mainly formed in the disordered macroporous materials at La/Zn=1 and 2. In contrast, the conventional coprecipitation of La2O2CO3/ZnO materials dominantly formed a hexagonal La2O2CO3 phase with aggregating morphology of ZnO and La2O2CO3 nanoparticles. However, nanocrystalline sizes of ZnO (7-10 nm) and monoclinic La2O2CO3 (12-14 nm) in the disordered macroporous structure were much smaller than those (29-36 nm for ZnO and 44-58 nm for hexagonal La2O2CO3) by conventional co-precipitation. In addition, the high temperature calcination at 700 °C increased the ZnO nanocrystallite size (24 nm) in the disordered macroporous framework, with transforming La2O2-CO3 into La2O3. This result implies that the interaction between monoclinic La2O2CO3 and ZnO in the disordered macroporous structure inhibited ZnO nanoparticle agglomeration.