We have developed a method for the synthesis of metal oxide nanocrystals with controllable shape and size, which is based on the direct thermal decomposition of metal nitrates in octadecylamine. Mn3O4 nanoparticles and nanorods with different lengths were synthesized by using manganese nitrate as the decomposition material. Other metal oxide nanocrystals such as NiO, ZnO, CeO2, CoO, and Co3O4 were also prepared by this method. These nanocrystals were then assembled into 3D colloidal spheres by a surfactant-assisted self-assembly process. Subsequently, calcination was carried out to remove the surfactants to obtain mesoporous metal oxides, which show large pores, good crystallization, thermally stable pore mesostructures, and potential applications in various fields, especially in catalysis and lithium-ion batteries.