Significance The activity of various 2-aminoarenethiolato-copper(I) (CuSAr) (pre-)catalyst was explored in the arylation of amines and N-containing heterocycles with aryl and heteroaryl bromides. These CuSAr (pre-)catalysts are thermally stable, soluble in common organic solvents, and show good catalytic activities in these N-arylations with catalyst loadings of 2.5 mol%.