<p>Few elements exemplify the duality of chemistry—where utility and toxicity depend on application—as strikingly as arsenic. Throughout history, arsenic has played a pivotal role in human civilization, and its influence endures in modern science through organoarsenicals, compounds featuring As–C bonds. However, the synthesis of these molecules has long been constrained by multistep processes reliant on hazardous arsenical reagents, limiting their practical adoption. Here we show a transformative mineral-to-molecule approach that leverages photoredox catalysis to directly convert naturally occurring arsenic sulfide minerals—particularly orpiment (As₂S₃)—into diverse organoarsenicals under visible-light irradiation. By reacting mineral-derived arsenic with organic iodides, our method bypasses toxic intermediates, enabling the efficient, one-step construction of functionalized arsenicals with broad structural diversity. Demonstrated across a wide range of substrates, this strategy establishes a safe, sustainable and scalable route to organoarsenicals, overcoming long-standing challenges in arsenic chemistry. Bridging geochemistry and synthetic chemistry, our work provides a blueprint for eco-friendly molecular manufacturing, transforming Earth’s mineral resources into high-value functional molecules.</p><p></p>