An efficient, mild, green, and metal-free protocol for the synthesis of quinoxaline from sulfoxonium ylides and o-phenylenediamines in the presence of N-iodosuccinimide (NIS) at room temperature has been developed. This operationally simple protocol avoids hazardous catalysts or oxidants, tolerates diverse functional groups, and delivers products in good to excellent yields with high atom economy. The scalable procedure holds promise for applications across pharmaceuticals, biotechnology, materials science, and agriculture, offering an efficient route to novel bioactive molecules and cost-effective drug discovery.