Solar energy harvesting and hydrogen economy am the two most important green energy endeavors for the future. However, a critical hurdle to the latter is how to safely and densely store and transfer hydrogen. Herein, we developed a reversible hydrogen storage system based on low-cost liquid organic cyclic hydrocarbons at room temperature and atmospheric pressure. A facile switch of hydrogen addition (>97% conversion) and release (>99% conversion) With superior capacity of 7.1 H-2 wt % can be quickly achieved over a rationally optimized platinum catalyst with high electron density, simply regulated by dark/light conditions. Furthermore, the photodriven dehydrogenation of cyclic alkanes gave an excellent apparent quantum efficiency of 6.0% under visible light illumination (420-600 nm) without any other energy input, which provides an alternative route to artificial photosynthesis for directly harvesting and storing solar energy in the form of chemical fuel.