We propose a two-steps photocatalytic deposition method to synthesize hierarchical Au nano- and microstructures on TiO2 surface. While the first deposition leads to the formation of flower-like Au microstructures on a highly active TiO2 thin film, needle-like sharp Au nanostructures are grown on the former Au microstructures after the second deposition. TiO2 surface decorated with hierarchical Au structures exhibits a superhydrophilic state with a contact angle (CA) below 5. After the modification of Au-TiO2 surface by octadecyl-phosphonic acid (ODP)-self-assembly monolayer (SAM), an extreme water-repellency (with CA > 163 degrees) is achieved which retains its stability even after multiple low-high temperature cycles. The spatially controlled photocatalytic decomposition of OPD-SAM on TiO2 thin film allows a superhydrophilic-superhydrophobic patterning which may open lot of application avenues in microfluidics, oil-water separation including in water harvesting technologies.