The pre‐existing Fermi level alignment between ZnO and CuSCN semiconductors gives rise to the two key elements needed for a self‐powered, binary‐response UV‐ sensor: photovoltaic behavior and low turn‐on bias. Nanosecond response times, self‐powered performance, and long‐term stability, coupled with scalable, inexpensive fabrication on the nanoscale, offer currently unmatched progression towards self‐sufficient nanoscale systems.