A noble-metal free and surface defect-induced mesoporous mixed valent NiO decorated TiO2 heterostructure with tuned bandgap has been successfully prepared. Its outstanding visible-light driven hydrogen evolution and its excellent H-2 storage ability have been examined and confirmed. The formation of oxygen vacancies by surface defect creates the Ni3+ and Ti3+ on the interface of the heterostructure induce the efficient H-2 evolution, benchmarked by 1200% enhancement in catalytic performance. The underlying chemistries include the near-unity occupancy of e(g) orbital (t(2g)(6) e(g)(1)) of Ni3+ which speeds up the electron transfer and significantly promote the excellent electron-hole separation efficiency, establishes the outstanding overall charge-transfer efficiency and long-term photocatalytic activity in the visible light spectrum. Multiple Ti3+ adsorption centers in the structure attract multiple intact H-2 molecules per each center via a sigma - pi bonding motif - namely the Kubas interaction - which leads to 480% higher H-2 adsorption capability against the performance of the pristine mesoporous TiO2. Not only the significant results, the study also provide an air-stable synthetic method on the basis of low-cost and abundant materials, which are strongly favoured for scaling up production.