It is rather challenging to develop photocatalysts based on narrow band-gap semiconductors for water splitting under solar irradiation. Herein, we synthesized the Cu2O/Cu2Se multilayer heterostructure nanowires exposing {111} crystal facets by a hydrothermal reaction of Se with Cu and KBH4 in ethanol amine aqueous solution and subsequent annealing in air. The photocatalytic H-2 production activity of Cu2O/Cu2Se multilayer heterostructure nanowires is dramatically improved, with an increase on the texture coefficient of Cu2O(111) and Cu2Se(111) planes, and thus the exposed {111} facets may be the active surfaces for photocatalytic H-2 production. On the basis of the polar structure of Cu2O {111} and Cu2Se {111} surfaces, we presented a model of charge separation between the Cu-Cu2Se(111) and O-Cu2O((1) over bar (1) over bar (1) over bar) polar surfaces. An internal electric field is created between Cu Cu2Se(111) and O-Cu2O((1) over bar (1) over bar (1) over bar) polar surfaces, because of spontaneous polarization. As a result, this internal electric field drives the photocreated charge separation. The oxidation and reduction reactions selectively occur at the negative O-Cu2O((1) over bar (1) over bar (1) over bar) and the positive Cu Cu2Se(111) surfaces. The polar surface-engineering may be a general strategy for enhancing the photocatalytic H-2-production activity of semiconductor photocatalysts. The charge separation mechanism not only can deepen the understanding of photocatalytic H-2 production mechanism but also provides a novel insight into the design of advanced photocatalysts, other photoelectric devices, and solar cells.