Octopamine is a phenol analog of noradrenaline and acts as a neurotransmitter in invertebrates such as octopus. It is available as a hydrochloride salt to avoid air oxidation. We applied laser desorption supersonic jet technique to octopamine hydrochloride without any chemical preparations and found that molecular ion of octopamine, not salt, is observed. Resonance-enhanced 2-photon ionization and ultraviolet-ultraviolet hole-burning spectra of octopamine were measured, and four conformers were identified. This number of conformations is rationalized by conformations of ethanolamine chain and orientations of phenolic OH.