The direct coupling of light harvesting and charge storage in a single material opens new avenues to light storing devices. Here we demonstrate the decoupling of light and dark reactions in the two-dimensional layered niobium tungstate (TBA)(NbWO) for on-demand hydrogen evolution and solar battery energy storage. Light illumination drives Li/H photointercalation into the (TBA)(NbWO) photoanode, leading to small polaron formation assisted by structural distortions on the WO sublattice, along with a light-induced decrease in material resistance over 2 orders of magnitude compared to the dark. The photogenerated electrons can be extracted on demand to produce solar hydrogen upon the addition of a Pt catalyst. Alternatively, they can be stored for over 20 h under oxygen-free conditions after 365 nm UV illumination for only 10 min, thus featuring a solar battery anode with promising capacity and long-term stability. The optoionic effects described herein offer new insights to overcome the intermittency of solar irradiation, while inspiring applications at the interface of solar energy conversion and energy storage, including solar batteries, "dark" photocatalysis, solar battolyzers, and photomemory devices.