Solar energy is potentially the largest source of renewable energy for providing electrical power for human society. However, significant advances are required to make photovoltaic technologies have a low-carbon footprint in manufacture, be environmentally friendly at the end of their lives through recyclability, and be biodegradable. Here we report dissolvable organic photovoltaic devices based on poly(2-hydroxyethyl methacrylate), which show equal power conversion efficiency to their glass substrate-based counterparts. We use a novel method of including smectic liquid crystal (7-dioctyl[1]benzothieno[3,2- b][1]benzothiophene, C8-BTBT) as a crystal phase regulator in the heterojunction donor:acceptor polymer system to maintain the disposable organic solar cell efficiency without pre- or post-thermal annealing. The results show strong promise not only for more sustainable solar-cell fabrication but also as disposable and biocompatible solar cells for self-powered (energy harvesting) wearable and biomedical devices.