Rotational spectroscopy has primarily been used to investigate fundamental aspects of molecular physics. It is a uniquely precise tool for the determination of molecular structure in gas-phase molecules.  It can be used to establish barriers to internal rotation such as that associated with the rotation of the  group relative to the  group in chlorotoluene (). When fine or hyperfine structure can be observed, the technique also provides information on the electronic structures of molecules. Much of current understanding of the nature of weak molecular interactions such as van der Waals, hydrogen and halogen bonds has been established through rotational spectroscopy. In connection with radio astronomy, the technique has a key role in exploration of the chemical composition of the interstellar medium. Microwave transitions are measured in the laboratory and matched
to emissions from the interstellar medium using a radio telescope.  was the first stable polyatomic molecule to be identified in the interstellar medium. The measurement of chlorine monoxide  is important for atmospheric chemistry. Current projects in astrochemistry involve both laboratory microwave spectroscopy and observations made using modern radiotelescopes such as the Atacama Large Millimeter/submillimeter Array (ALMA).