Concerning the aryl bromid, the reaction proceeded smoothly with a wide array of substrates to provide the corresponding products in moderate to high yields with universally high enantioselectivities. Notably, electron-deficient or electron-rich arenes were amenable coupling partners, in which the substituent could be placed at para and meta position. A variety of functionalities such as a nitrile (2b), trifluoromethyls (2c, 2p, 2r), esters (2d, 2m, 2q), halides (2f, 2g, 2n, 2o), ethers (2i, 2j) were all readily accommodated. Despite the ability of nickel complex to activated aryl chlorides, our approach could tolerate Ar-Cl groups (2f, 2o). In particular, sensitive functional groups including easily reduced ketone (2a) and aldehyde (2e), and triflate (2k) and boronic acid pinacol ester (2l) commonly used for cross-coupling, all remained intact under the standard reaction conditions. Furthermore, the pharmaceutically important heterocycle-pyridine (2r) was compatible as well. Next, we sought to survey the influence of the N-vinylindole variants that could be used in the catalytic hydroarylation event. Delightfully, a diverse array of functional groups were suitable at different positions on the benzene ring of the indole, including a 6-methoxy (3s), 6fluoro (3t), 6-cyano (3u), and 5-methyl (3v) substituent. It is worth noting that alkyl group at the C3-position of the indole scaffold was accommodated, delivering the corresponding product 3w in moderate yield but with excellent enantioselectivity, which is difficult to obtain employing previous CuH catalysis. In addition, carbazole-derived substrate afforded the deisired Nalkylated product in moderate yield and enantioselectivity (3x). Gratifyingly, a diverse set of more sterically hindered cis-β-substituted N-alkenyl indoles were also successfully transformed utilizing this method, and the corresponding N-alkylindoles were readily prepared in useful yields with good levels of enantioselectivity (3y-3dd). Of note, the C-C bond-forming event occurs regioselectively at the carbon α to the nitrogen of indoles, even in the presence of other directing groups such as amide (3z-3bb), ester (3cc), and aryl (3dd). Especially, this modular reaction could be applied to prepare important serotonin reuptake inhibitor derivatives with good efficiency and enantioselectivities (3z-3bb, 81-92% ee's).