Despite the C-H functionalization of arenes offering an efficient synthetic route towards functionalized aromatic compounds with high atom- and step-economy, the low reactivity of the C-H bond makes this transformation rather challenging. Compared with mono-metal catalysis, the introduction of bimetallic catalysis would greatly enhance the reactivity and selectivity of this transformation. In this review, we highlighted recent progress on C-H functionalization of arenes via NHC-Ni/Al catalysis. The added aluminum as a co-catalyst would activate arene through Lewis acid-base interaction, and regioselectivity could be controlled through the synergism of NHC-Ni and Al. And this strategy could be also applied in enantioselective C-H alkylation with well-designed chiral NHC ligands.