A Cu(II)-catalyzed, effective C–N coupling of 2-aminobenzothiazoles with boronic acids in acetonitrile under open vessel chemistry was achieved. This protocol demonstrates the N-arylation of 2-aminobenzothiazoles with a broad range of differently substituted phenylboronic acids at room temperature and accomplishes moderate to excellent yields of the desired products. Under the optimized condition, phenylboronic acids bearing halogen at the para and meta positions were found to be more fruitful.