As a readily available feedstock, styrene with about 25 million tons of global annual production serves as an important building block and organic synthon for the synthesis of fine chemicals, polystyrene plastics, and elastomers. Thus, in the past decades, many direct transformations of this costless styrene feedstock were disclosed for the preparation of high-value chemicals, which to date, generally performed on the functionalization of styrenes through the allylic C-H bond, C(sp2 )-H bond, or the C=C double bond cleavage. However, the dealkenylative functionalization of styrenes via the direct C-C single bond cleavage is so far challenging and still unknown. Herein, we report the novel and efficient C-C amination and hydroxylation reactions of styrenes for the synthesis of valuable aryl amines and phenols via the site-selective C(Ar)-C(alkenyl) single bond cleavage. This chemistry unlocks the new transformation and application of the styrene feedstock and provides an efficient protocol for the late-stage modification of substituted styrenes with the site-directed dealkenylative amination and hydroxylation.