Selective functionalization of allylic C-H bonds into other chemical bonds with Zselectivity are 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 thiathrenium salts. Notably, the reaction preferably provides multialkyl substituted allylic amines, esters, and ethers with Z-selectivity. 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.