The catalytic activity of V2+/V3+ and VO2+/VO2 + redox couples on the halogen-doped graphene nanoplatelets (F-, Cl-, and Br-GNPs) is studied by ball-milling graphite flakes with fluorine (F2), chlorine (Cl2), and bromine (Br2) molecules, respectively. Using the edge-selectively halogenated graphene materials with different edge exfoliation degrees, the vanadium redox reactions can be significantly facilitated by having abundant edge defects with large surface area in the order: Br-GNP>Cl-GNP>F-GNP. The influence of halogen functionalization on graphene nanoplatelets towards vanadium redox couples is further confirmed by stack-type vanadium redox flow batteries that demonstrates better cell performance than graphene nanoplatelets without dopant at the edges. Notably, the Br-GNP showed unique electrochemical performance of increased initial charge/discharge capacity and improved rate capability, respectively. It was found that halogen doping on graphene-based materials can promote vanadium redox reactions by creating effective active sites, and the electrocatalytic activity is dependent on edge exfoliation degree and well-preserved basal planes.