Catalyst- and additive-free reactions for synthesizing valuable organic compounds have garnered significant attention in the context of sustainable development. As crucial structural motifs, allylic sulfones find extensive applications in pharmaceutical development and organic synthesis. Despite remarkable advances in allylic sulfone construction, catalyst-free and additive-free methodologies remain an underexplored frontier. Herein, we present an environmentally benign and atom-economical approach for synthesizing allylic sulfones by reacting electron-rich aryl-1,3-dienes with sulfinic acids, achieving yields of 10–94%. This transformation proceeds under ambient air at room temperature, eliminating the need for catalysts or additives. The protocol demonstrates exceptional regio- and chemo-selectivity, streamlined operational simplicity, and excellent scalability potential. This methodology establishes a sustainable and cost-effective paradigm for allylic sulfone synthesis, aligning with green chemistry principles.