Highly efficient photocatalytic reduction of environmental pollutants requires the enrichment of photogenerated electrons on the photocatalyst's surface. Thus, proper material design and modification are needed to efficiently separate photogenerated electron/hole pairs and achieve their oriented migrations for the enrichment of photogenerated electrons on their surface. In this work, a modified photo-deposition process was developed which successfully deposited silver nanoparticles selectively on {1 0 1} facets of TiO2 nanocrystals with co-exposed {0 0 1}/{1 0 1} facets. The synergistic effect of crystal facet engineering and the selective deposition of silver nanoparticles on {1 0 1} facets largely enhanced the separation of photogenerated carriers and enriched the presence of photo-generated electrons onto the surface of TiO2 to a net negative-charged surface. A strong photocatalytic reduction capability of the sample was demonstrated by its superior photocatalytic reduction activity on aqueous nitrate under a simulated solar illumination. The removal ratio of aqueous nitrate reached similar to 95%, and most of the reduction product was the desirable N-2 with the selectivity over 90%. These TiO2 nanocrystal with co-exposed {0 0 1}/{1 0 1} facets and silver modification on {1 0 1} facets could also effectively remove both nitrate and various organic pollutants from water simultaneously. (C) 2015 Elsevier B.V. All rights reserved.