Compounds containing bibenzochalcogenophene structures are provided in which the chalcogenide is sulfur, selenium, or tellurium. The compounds are characterized by planarity, rigid conjugation structure and high charge mobility making them useful as organic semiconductor in optical devices, electronic devices and integrated devices like organic field effect transistors (OFET) for thin film transistor liquid crystal display (LCD), electrophoretic display such as electronic paper, organic light emitting diode (OLED) for flat panel displays, organic radio frequency identification (ORFID) tags, organic photovoltaic (OPV), sensor devices, and analog and digital electronics.