Triarylamine has been widely used in opto- and electro-active materials for its good electron donating and transporting capability, as well as its special propeller starburst molecular structure. Recently, organic photovoltaic functional materials with triarylamine as electron donor have aroused great interest and become the focus of intensive research in the field of solar cells. These materials have significantly reinforced the conversion efficiency of next-generation solar cells, especially dye sensitized solar cells. This Feature Article describes new synthetic methods and the application of starburst triarylamines, highlighting the applications in photovoltaic and optoelectrical fields.