Efficient interfacial exciton transfer and separation have been regarded as the foremost confront of semiconductor oriented photocatalysis. The simultaneous discovery of crystal facet isotype heterojunction across the (040)-reduction and (110)-oxidation facet of monoclinic scheelite BiVO4 crystal; and Schottky junction at the interfacial region of BiVO4 crystal with well-exposed functional (040) facet and r-GO sheets has been reflected as an efficient electron injection route. In this context lucrative architecture of a high productive all-solid-state Z-scheme charge transfer dynamics In2S3@r-GO@(040/110)-BiVO4 isotype ternary hybrid photocatalyst was carried out and well-validated by FESEM and HRTEM analyses. Photoelectrochemical measurements have revealed that the accumulated photo-electrons over the exposed (040)-crystal facet of BiVO4 truncated bipyramid easily cross the minor Schottky junction to expedite the unidirectional injection to the pi-pi conjugated two-dimensional planar r-GO structure. Besides, subsequent trapping of the injected electrons by the photoinduced holes of In2S3 leading to a superior charge carrier separation in the material, validated by PL, EIS, Mott-Schottky, and transient photocurrent analysis. Perceptibly, this intimate interfacial interacted crystal facet dependent electron shuttle provided a longer life span electrons and holes to settle in the conduction band of In2S3 and valence band of (110)-BiVO4, respectively, for elevated photo-activity efficiency. The In2S3@r-GO@(040/110)-BiVO4 ternary hybrid contributes 89.7% of Ciprofloxacin (CIP) detoxification in 150 min and 885.43 mu mol of O-2 evolution in 120 min. More in, the constructive interrelations of resultant Physico-chemical, photoelectrochemical, and augmented photocatalytic redox efficiency were well-illustrated. This unique association semiconductor ternary hybrid photocatalyst via metal-free mediating agent crystal-facet sandwich structure will provide a scientific innovative basis for rational design and realization of advanced Z-scheme photocatalytic system for energy and environment application. (C) 2020 Elsevier Inc. All rights reserved.