The direct sequential arylation reaction at the C3 and C1 positions of imidazo[1,5-a]pyridines with a variety of aryl iodides catalyzed by [Pd(phen)(2)](PF6)(2) is described. The reaction of unsubstituted imidazo[1,5-a]pyridine with various aryl iodides proceeded selectively at the C3 position to exclusively give the corresponding C3-arylated products. The one-pot double-arylation reaction at the C3 and C1 positions of unsubstituted imidazo[1,5-a]pyridine with different aryl groups was also achieved.