Novel star-shaped hole transporting materials with a triazine unit have been synthesized. When the new Triazine-Th-OMeTPA was used as a hole transporting material in perovskite solar cells, the power conversion efficiency reached 12.51% under AM 1.5 G (100 mW cm(-2)) illumination, showing competitive photovoltaic performance with the widely used spiro-OMeTAD based solar cell (13.45%).