Solution-processed organic/inorganic hybrid solar cells have emerged as a new platform for low-cost optoelectronics. At the heart of photovoltaic devices lies the matching of a junction, which requires the suitable energy level alignment of n-type and p-type semiconductors. Incorporating foreign ions into bulk semiconductors has been largely employed for many decades, yet electronically active doping in energy level Control of the hybrid bulk heterojunctions has been rarely involved and the demonstration of robust functional optoelectronic devices had thus far been elusive. Herein, we introduce Ru ions into TiO2 to decorate the energy level of the acceptor to gain better energy level alignment between the donor and acceptor. By reducing the 'excess' energy offset between the n-type and p-type semiconductors, the electron transfer becomes faster, thus leading to a notable enhancement in power conversion efficiency, i.e., from 2.20% to 2.89%. The results demonstrate that the energy level can be controlled effectively by the versatile Ru dopants. This work opens an effective route for accelerating the charge carrier transfer at the interface and achieving high-performance organic/inorganic hybrid optoelectronic devices. (C) 2014 Elsevier B.V. All rights reserved.