The present thesis shows how versatile and important the field of gas-phase spectroscopy under supersonic expansion conditions can be to understand fundamental intermolecular and intramolecular interactions. We have employed spectroscopic techniques over a very broad range spanning from microwave (2-18 GHz), through infrared (2600-4000 cm-1) and ultraviolet (350-250 nm) region, studying therotational, vibrational and electronic properties,respectively. These techniques use either chirped-pulse based (broadband rotational spectroscopy) or laser based methods (vibrational and electronic spectroscopy), and their usage depends on the types of information of particular interest and the chemical system requirements of specific techniques. The analytes are brought into the gas phase and supersonically cooled to their zero-point vibrational level to perform rotational and vibrationallyresolved IR/UV spectroscopy, including conformer-specific techniques. The variety of small organic molecular systemsstudied include phenyl-containing hydrocarbons, water containing clusters, heteroatom containing organic molecules with and without phenyl ring, fused aromatic molecules, bichromophoric molecules and pyrolysis reaction intermediates. Apart from gaining invaluable fundamental knowledge of the various interactions, we also observe interesting quantum-physical phenomena like tunneling and large amplitude motions that provide further insight into the molecular world.