The role of various neurotransmitter systems in the brain in extinction behavior is examined. An attempt is made to suggest psychological mechanisms (such as attention, secondary reinforcement or internal inhibition) by which the neurotransmitter systems or drugs act to produce the observed alteration in extinction behavior. The putative neurotransmitters acetylcholine, noradrenaline, dopamine, serotonin, endorphins and the peptides are reviewed, as are pharmacological agents such as the benzodiazepines, the barbiturates, the psychodelics, the neuroleptics, the psychomotor stimulants and cannabinoids. Other treatments and factors are considered such as peripheral hormones and the adrenal-pituitary axis. It is suggested that the noradrenergic system may be involved in the expression of extinction behavior by a role in selective attention, the dopamine system via an involvement with secondary reinforcement, the cholinergic system by a mechanism of response inhibition and the barbiturates and benzodiazepines by a block of nonreward.