In this work, the Mobius strip-like reduced graphene oxide (RGO) was fabricated via I-3(-) and I-5(-) clusters, which offered a route for electron tunneling over RGO. This flip-flop electron tunneling took place via strong Rashba spin-orbit coupling between polyiodides and C atoms of RGO by the active electrons of polyiodides living in the p orbitals and it could bridge the easier charge transfer route between far-located carbon atoms at the edges of RGO through the polyiodides. This tunneling also restrained effectively the anisotropy of the electron transfer over RGO surface, achieving the rapid and efficient electron transfer over the surface of the RGO, resulting in remarkable increase of RGO conductivity and enhancing the lifetime of photogenerated charges. With the help of these properties, the obtained I-RGO/Ag photocatalyst presented a high H-2 generation activity under visible light irradiation. 318.8 mu mol H-2 was evolved over I-RGO/Ag photocatalyst in 3 h, about 3.3 time higher than that of un-iodine RGO/Ag. In addition, no remarkable decay of H-2 evolution activity was observed in 1080 min reaction. The highest apparent quantum efficiencie (AQE) value of 28.8% was achieved at 430 nm. (C) 2017 Elsevier B.V. All rights reserved.