The scanning electrochemical microscope was applied in the feedback mode to deposit Au microstructures on n-Si(111) and indium-tin oxide. This was accomplished by the anodic dissolution of An at the microelectrode followed by the subsequent redeposition of the Au on the substrate. The influence of pH, substrate potential, and deposition time on the crystalline nanometer structure of the micrometer Au deposits was investigated. The effect of these parameters on deposition could be explained by the band structure of the silicon. Moreover, understanding the role played by the different parameters allows depositing predefined nanocrystalline structures.