Silicon (Si) doped anatase titanium dioxide (Ti(0.89)Si(0.11)O(2)) single crystals bound by high-index {201} facets and high-energy {001} facets were synthesized by a facile method. It was found that the Si-doping can widely extend the optical absorption edge into the visible-light region and highly reactive facets can enhance their photocatalytic activity, as revealed by the combination of experimental and computational studies.