The construction of photocatalytic systems that have strong redox capability, effective charge separation, and large reactive surfaces is of great scientific and practical interest. Herein, an edge-connected 2D/2D Z-scheme system that combines the facet junction and the interfacial heterojunction to achieve effective long-range charge separation and large reactive surface exposure is designed and fabricated. The heterostructure is realized by the selective growth of 2D-layered MoS 2 nanoflakes on the edge-sites of thin TiO 2 nanosheets via an Au-promoted photodeposition method. Attributed to the synergetic coupling of the facet junction and the interfacial heterojunction that assures the effective charge separation, and the tremendous but physically separated reactive sites offered by layered MoS 2 and highly-exposed (001) facets of TiO 2 , respectively, the artificial Z-scheme exhibits excellent photocatalytic performance in photodegradation tests. Moreover, the junctional plasmonic Au nanoclusters not only act as electron traps to promote the edge-selective synthesis but also generate "hot electrons" to further boost photocatalytic performance. The Z-scheme charge-flow direction in the heterostructure and the roles of electrons and holes are comprehensively studied using in situ irradiated X-ray photoelectron spectroscopy and photodegradation tests. This work offers a new insight into designing high-performance Z-scheme photocatalytic systems.