Metal-assisted chemical etching (MACE) is a widely applied process for fabricating Si nanostructures. As an electroless process, it does not require a counter electrode, and it is usually considered that only holes in the Si valence band contribute to the process. In this work, a charge carrier collecting p-n junction structure coated with silver nanoparticles is used to demonstrate that also electrons in the conduction band play a fundamental role in MACE, and enable an electroless chemical energy conversion process that was not previously reported. The studied structures generate electricity at a power density of 0.43 mW/cm2 during MACE. This necessitates reformulating the microscopic electrochemical description of the Si-metal-oxidant nanosystems to separately account for electron and hole injections into the conduction and valence band of Si. Our work provides new insight into the fundamentals of MACE and demonstrates a radically new route to chemical energy conversion by solar cell-inspired devices.