Transition metal oxides with nanoscale or special micro-structures are favoured both in scientific research and industry application. Although many methods are developed, there is still a need and a potential payoff for developing a novel and convenient synthetic method. Inspired by nature hydrothermal vent, herein, we develop an ingenious “top-down” method to prepare various transition material compounds, which have diverse and fascinating structures. Our design thought is to etch the A ions by acid from the precursor AxMyOz (A=alkaline and alkaline earth metal, M=transition metal) and leave the MOn/2 or HMO(n+1)/2 behind under the hydrothermal condition. As a result, we obtain various structures like amorphous mesoporous bulk Nb2O5, morphology-re- tained bulk HNbO3 and ZrO2, monodispersed ZrO2 nanoparticles, assembled porous ZrO2 nanostructure, hollow TiO2, and the derived core-shell structure. These materials have great potential application in catalysis and energy storage. We employed hollow TiO2 cube as the high cut-off anode of lithium-ion batteries and harvested excellent performance. After these fruitful attempts, we have found that etching AxMyOz to obtain transition metal compound is a complex reaction containing some different competing reactions, thus allowing us to regulate and control the microstructure of the products by adjusting the reaction condition. We believe there are more interesting structures waiting to be fabricated by similar “top-down” method and these unique materials have great potential in many fields.