A hexagonal-close-packed (hcp), hierarchical amorphous TiO2 nanocolumn array was fabricated by pulsed laser deposition (PLD) using a PS colloidal monolayer as a template under a high pressure (6.7 Pa) of background oxygen gas. The formation mechanism was investigated, and a model of multidirection glancing deposition was proposed to explain the formation process. This strategy can be extended to the fabrication of similar structures using different materials. Interestingly, this nanostructured array could be transferred to almost any substrate, avoiding restriction of substrate types in fabrication of nanocolumn arrays, which is helpful in the design and creation of nanodevices on various desired substrates. This hierarchical nanocolumn array exhibits excellent superamphiphilicity with both water and oil contact angles of 0 degrees, without further UV irradiation. More importantly, the amorphous TiO2 nanocolumn array demonstrates better performance in photocatalytic activity than an anatase nanocolumn array due to its large surface area and special microstructures, suggesting that the surface area of the TiO2 is preferable to its crystal structure for enhancing photocatalytic activity. The combination of superamphiphilicity and pholocatalytic activity gives the surface an excellent self-cleaning effect.