Recent discovery of bulk insulating topological insulator (TI) Bi2- xSbxTe3- ySey paved a pathway toward practical device application of TIs. For realizing TI-based devices, it is necessary to contact TIs with a metal. Since the band-bending at the interface dominates the character of devices, knowledge of TIs' work function is of essential importance. We have determined the compositional dependence of the work function in Bi2- xSbxTe3- ySey by high-resolution photoemission spectroscopy. The obtained work-function values (4.95-5.20 eV) track the energy shift of the surface chemical potential seen by angle-resolved photoemission spectroscopy. The present result serves as a useful guide for developing TI-based electronic devices.