Graphitic carbon nitride (g-C3N4) is a fascinating polymeric organic semiconductor and has attracted extensive interests from researchers during the past few decades. This work focused on a g-C3N4/TiO2 composite with high percentage of {001} facets. We confirmed that composites of g-C3N4/TiO2 with close interfacial connections between g-C3N4 and TiO2 had been formed and made up of reactive {001) TiO2 crystal facets. It also presented significantly enhanced photocatalytic ability toward to RhB degradation, gaseous acetone photoconversion and hydrogen evolution under visible light irradiation. Active species trapping experiments indicated that O-2(center dot-) played a most important part in catalytic process. It was also pointed out that the enhanced photocatalytic efficiency could be attributed to the interfacial connections between g-C3N4 and TiO2, which efficiently transferred the photocarriers. Copyright (C) 2016, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.