Abstract: Industrial-scale ethylene production occurs primarily by fossil-powered steam cracking of ethane—a high-temperature, high-energy process. An alternative, photochemical, pathway powered by sunlight and operating under ambient conditions could potentially mitigate some of the associated greenhouse gas emissions. Here we report the photocatalytic dehydrogenation of ethane to ethylene and hydrogen using LaMn1−xCuxO3. This perovskite oxide possesses redox-active Lewis acid sites, comprising Mn(III) and Mn(IV), and Lewis base sites, comprising O(-II) and OH(-I), collectively dubbed surface-frustrated Lewis pairs. We find that tuning the relative proportions of these sites optimizes the activity, selectivity and yield for ethane dehydrogenation. The highest ethylene production rate and ethane conversion achieved were around 1.1 mmol g−1 h−1 and 4.9%, respectively. We show a simple outdoor prototype to demonstrate the viability of a solar ethylene process. In addition, techno-economic analysis revealed the economic potential of an industrial-scale solar ethylene production from ethane.