The combination of heterogeneous inorganic nanocrystals provides novel nanometer-scale architectures for exploration of novel functions. In the present study, heterogeneous bilayers, such as BaTiO3-Fe3O4 and Mn3O4-CeO2, are fabricated via layer-by-layer stacking of several rectangular nanoblocks 5-23 nm in size by evaporation-driven self-assembly. Specific heterojunctions between inorganic crystals are constructed by nanoscale simple brick work through spontaneous adjustment of the crystallographic orientations of the nanoblocks in the lower and upper layers.