Chalcopyrite and chalcogenide crystals are investigated for optical rectification and electro-optic sampling. Broadband and narrowband terahertz radiation is produced using ZnGeP2, CdSiP2, and AgGaSe2 chalcopyrite crystals, as well as a BaGa4Se7 chalcogenide crystal. Broadband terahertz radiation is detected using a ZnGeP2 chalcopyrite crystal. We envision these crystal classes being used to generate and detect terahertz radiation in research and commercial applications.