Double-layered ZnO nanostructures have been synthesized by aqueous solution method on (001) plane of ZnO nanorod. A stepwise changing of aqueous solution concentration gave rise to a new nano-structured layer consisting of either multiple of nanorods or nanowires with much smaller radii than that of the ZnO nanorod on which the new layer was grown. As the first step the ZnO nanorods have been grown to have the (001) preferential orientation in the aqueous solution consisting of 0.1M zinc nitrate and 0.1 M HMT. This preferentially aligned ZnO nanorods have been regrown in either a less diluted solution of 0.01M zinc nitrate and 0.01 M HMT or a more diluted solution of 0.005M zinc nitrate and 0.01 M HMT. A new nano-layer consisting of numerous aligned nanorods or nanowires has been produced on the (001) planes of ZnO nanorods. The growth mechanism for this double layered ZnO nanostructure is ascribed to the (001) polar surface energy instability and inhibition of (001) plane growth due to the step-wise change of aqueous solution concentration; ZnO nuclei formed on the (001) plane grow preferentially in (010) plane instead of (001) plane to reduce the total surface energy. Surface area of ZnO nanostructure can be increased in orders of magnitudes by forming a new layer consisting of smaller nanorods/nanowires on (001) plane of ZnO nanorods.