The higher reactivity of the C4-H bond as compared to the C5-H bond of 1,2,3-trifluorobenzene in palladium-catalyzed direct arylation allows the selective synthesis of 4-aryl-1,2,3-trifluorobenzenes in moderate to high yields. In most cases, phosphine-free Pd(OAc)2 catalyst and inexpensive KOAc base were employed. Then, from these 4-aryl-1,2,3-trifluorobenzenes, the palladium-catalyzed C-H bond functionalization of the C6-position allows the synthesis of the corresponding 4,6-diarylated 1,2,3-trifluorobenzenes. We also applied these reaction conditions to the regioselective direct C3-arylation of 1,2,4-trifluorobenzene.