Multicomponent　reactions　represent　a　powerful　method　for　building　complex　molecules　from　structurally　simple　starting　materials.　Herein,　we　report　a　novel　three-component　radical-polar　crossover　reaction　involving　a　tandem　addition　reaction　of　two　different　olefins,　which　is　initiated　by　the　selective　addition　of　fluorosulfonyl　radicals　to　alkyl　alkenes.　This　tandem　process　provides　facile　and　effective　access　to　multiple　functionalized　aliphatic　sulfonyl　fluoride　molecules.　Further　transformation　of　the　products　is　also　demonstrated.　©　2023　American　Chemical　Society.