A white-light-emitting organogel is designed by the controlled self-assembly of a bischolesterol-functionalized OPV donor that allows slow energy migration and partial energy transfer in the gel state to an encapsulated acceptor. The white-light emission occurs because of the combination of blue-light emission from the OPV monomers, green-light emission from the OPV self-assembly, and red-light emission from the acceptor.