We introduce donor-acceptor substituted anthracenes as effective molecular solar thermal energy storage compounds that operate exclusively in the solid state. The donor-acceptor anthracenes undergo visible light-induced [4+4] cycloaddition reaction, producing metastable cycloadducts, dianthracenes with quaternary carbons, and storing photon energy. The triggered cycloreversion of dianthracenes to anthracenes discharges the stored energy as heat in the order of 100 kJ/mol (200 J/g). The series of compounds displays remarkable self-heating, or cascading heat release, upon the initial triggering. Such self-activated energy release is enabled by the large energy storage in dianthracenes, low activation energy for their thermal reversion, and effective heat transfer to unreacted molecules in the solid state. This process mirroring the self-ignition of fossil fuels opens up opportunities to use dianthracenes as effective and renewable solid-state fuels that can release energy rapidly and completely upon initial activation.