A heterogeneous catalytic system has been developed for synthesis of heteroaryl-substituted triphenylamine derivatives via a Pd/C-catalyzed aerobic and ligand-free Suzuki-Miyaura reaction of heteroaryl halides with 4-(diphenylamino)phenyl boronic acid (DPBA) in aqueous media. The reaction conditions (solvent, base, temperature and Pd/C loading) were optimized using a model cross-coupling reaction between 2-bromopyridine and DPBA. The optimal conditions were: 2-bromopyridine (0.25 mmol), DPBA (0.375 mmol), Pd/C (1.5 mol%), ethanol/water (4 mL, volume ratio of 3:1), K2CO3 (0.5 mmol) and 80 °C. Twelve triphenylamine derivatives were prepared with yields of 54-99% under the optimal conditions. The structures of the products were confirmed by 1H NMR. The reaction was performed under aerobic and aqueous conditions, and the catalyst was easily separated and recovered, therefore, this protocol is convenient and environmental benign for the preparation of important heteroaryl-substituted triphenylamine derivatives.