Crystal facet engineering and surface modification of semiconductor have become important strategies to improve photocatalytic activity by optimizing surface charge carrier separation/transfer and extending solar spectrum utilization. In this work, we report anatase single-crystalline TiO2 hollow tetragonal nano cones with large exposed (1 0 1) facets by a facile liquid-phase interfacial synthetic strategy, using the hydrolysis of tetrabutyltitanate with adscititious water in the organic solvent of cyclohexane and a capping agent of 1, 6-hexanediamine. The specific surface area of these TiO2 hollow tetragonal nanocones is as high as 331.3 m(2)/g. Thanks to large exposed (1 0 1) facets and high surface area, these TiO2 hollow tetragonal nanocones exhibited excellent full-arc photocatalytic activities for the degradation of organic pollutants. Remarkably, the butoxy group could be modified onto TiO2 hollow tetragonal nanocones through post-synthesis treatment in tetrabutyltitanate glycol solution, which brought about eximious visible light photocatalytic activities for the degradation of colored dyes of RhB and MO, especially for RhB, by virtue of much improved electron trapping ability of the Ti-O group from the excited dye due to the strong electronegativity of the oxygen atom in the butoxy group. This work advances us to rationally tailor the atomic and electronic structure of the photocatalyst for outstanding photocatalytic properties in various environmental and energy-related applications. (C) 2016 Elsevier Inc. All rights reserved.