The monoamine neurotransmitters have long been ascribed important modulatory actions on male sexual behavior by a wealth of pharmacological studies. Methodological developments have now made possible the assessment of the extracellular levels of amine transmitters and their metabolites in discrete brain areas of sexually behaving animals using in vivo voltammetry and microdialysis. Studies in our and other laboratories consistently show increased dopamine release in forebrain structures known to be involved in mating activity, including the nucleus accumbens and the medial preoptic area, during both the appetitive (i.e., non-contact exposure to sexual stimuli) and consummatory phases of this behavior. Serotonin utilization seems to be mainly related to consummatory events. These findings are consistent with the pharmacological evidence as well as previous ex vivo work. The state of sexual inactivity that follows unrestricted mating associates with increased dopamine turnover in the preoptic area. According to the available information, it could reflect some blockade of dopaminergic receptors, possibly involving prolactin. No disturbance of ongoing sexual behavior was observed during the neurochemical monitoring sessions with either methodology. These studies show voltammetry and microdialysis as powerful complementary tools for the assessment of sociosexual interactions.