A self-assembled monolayer of dithiol, namely 1,4-benzenedimethanethiol (BDT), on a polycrystalline gold surface was effectively used to carry out a two-dimensional reaction between pendent -SH and zirconium ion in solution to produce oriented monoclinic zirconia at room temperature on potentiodynamic cycling. Cyclic voltammetry (CV), X-ray diffraction (XRD), and scanning electron microscopy (SEM) were used to follow the monolayer formation, Zr-attachment on the SAM surface, and the subsequent formation of ZrO2 phase. The XRD analysis shows the growth of the crystal as monoclinic form with a size ranging from 5 to 15 mu m. A tentative reaction scheme and also a mechanism are proposed to understand the role of SAM in changing the size and habit during the crystallization of ZrO2 at room temperature.