An efficient nickel-catalyzed protocol for C-S cross-coupling through the direct functionalization of 2-aryl-1,2,3-triazole N-oxide C-H bonds with aryl or alkyl thiols, or diphenyl disulfide has been developed. The targeted N(+)-O(-) bond cleavage can be observed during the reaction, and thus obviates the need to use an additional deoxygenation step. This new protocol for the preparation of thiolated 2-aryl-1,2,3-triazoles appears to offer good yields with high regioselectivity, mild conditions, and a wide substrate scope.