Selective functionalization of allylic C–H bonds into other chemical bonds is among the most straightforward and attractive, yet challenging transformations. Herein, a transition-metal-free protocol for direct allylic C–H nitrogenation, oxygenation, and carbonation of alkenes by thianthrenation was developed. This operationally simple protocol allows for the unified allylic C–H amination, esterification, etherification, and arylation of vinyl thianthrenium salts. Notably, the reaction furnishes multialkyl substituted allylic amines, ammonium salts, sulfonyl amides, esters, and ethers in good yields. The reaction proceeds under mild conditions with excellent functional group tolerance and could be applied to late-stage allylation of natural products, drug molecules and peptides with excellent chemoselectivity.