The mechanism of nickel-catalyzed hydroarylation of styrenes has been explored with density functional theory. Instead of the stepwise pathway via a Ni(II)-H species, computational results unveil that the concerted RO-H oxidative addition/olefin insertion takes place kinetically favorable to generate the alkylnickel(II) species, which further undergoes transmetalation and reductive elimination to yield the hydroarylated product. The origins of regio- and stereoselectivity were revealed via analyzing the electronic and steric effects of the key transition states.