In this work, specific exposed crystal facets were employed to construct epitaxial heterostructure for high efficiency carriers transmission channel. The (001) face of anatase TiO2 was chosen to composite (001) Bi4Ti3O12 for two reasons. First, as the lattice spacing of (110) faces of anatase TiO2 (0.26741 nm) is very close to that of (020) (0.27240 nm) or (200) (0.27080 nm) faces of Bi4Ti3O12, (001) Bi4Ti3O12 will epitaxial grow on the (001) faces of anatase TiO2. Second, due to the high surface energy, the chemical reaction between TiO2 and Bi(NO3)3 will occur at a low Bi:Ti mole ratio to form well crystallographic Bi4Ti3O12 nanocrystals. Compared with Bi4Ti3O12/P25 composite, this epitaxial heterostructure is confirmed to be an ideal carriers exchange channel to extend the separation time of photo-induced carriers and enhance photocatalytic activity. This study demonstrates the importance of crystal facets choice of substrate for constructing high efficiency carriers transmission channel.