For the first time, g-C3N4@alpha-Fe2O3/Co-Pi heterojunctional hollow spheres were successfully fabricated via thermal condensation method followed by solvothermal and photo deposition treatment, which showed excellent photocatalytical property. Except for the Z-scheme charge transfer between alpha-Fe2O3 and g-C3N4, the Co-Pi could further reduce the combination of photogenerated electrons and holes as a hole storage agent, resulting in remarkably enhanced visible-light photocatalytic water splitting activity with the H-2 production rate of 450 mu mol h(-1)g(-1), which is 15.7 times higher than that of g-C3N4. Moreover, the photocatalytic activity of the prepared ternary hollow photocatalysts showed almost no significant weakness after five cycles, which indicated their good performance stability. The as-prepared g-C3N4@alpha-Fe2O3/Co-Pi also possessed good activity for overall water splitting with the hydrogen production rate reaching 9.8 mu mol h(-1)g(-1). This synthesized g-C3N4@alpha-Fe2O3/Co-Pi composite is expected to be a promising candidate for water splitting. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.