We present a novel point of view to fabricate an enhanced stability controllable growing, large-scale, direct, fast and template assisted nanostructure ZnO with twin –OH group terminated of compound containing –OH group by electrochemical deposition (ECD). In this paper, the collected potassium acid phthalate with twin –OH group was printed to form a matrix as template to synthesize a ZnO nanostructure. Structural analyses showed that the ZnO nanostructure is wurtzite in structure, without any secondary phases. Various features of Raman mapping and X-ray photoelectron spectroscopy of the as-prepared ZnO were found to mark variety of the characteristic of the as-prepared ZnO before and after tape test. A direct link between growing ZnO and potassium acid phthalate with twin –OH group was established, suggesting that this special twin –OH group between nanostructure ZnO and substrate (stainless steel) plays a vital role in forming a firm nanostructure ZnO film on the surface of the substrate. Furthermore, we raised a mechanism to explicate the functional process of twin –OH group on ZnO film. We believe that this facile method to fabricate a controllable nanostructure ZnO here is equally applicable to other semiconductors which are critical in optoelectronics, lasing and luminescence applications.