Multicomponent　reactions　represent　a　powerful　methodfor　buildingcomplex　molecules　from　structurally　simple　starting　materials.　Herein,we　report　a　novel　three-component　radical-polar　crossover　reactioninvolving　a　tandem　addition　reaction　of　two　different　olefins,　whichis　initiated　by　the　selective　addition　of　fluorosulfonyl　radicalsto　alkyl　alkenes.　This　tandem　process　provides　facile　and　effectiveaccess　to　multiple　functionalized　aliphatic　sulfonyl　fluoride　molecules.Further　transformation　of　the　products　is　also　demonstrated.