Intracranial self-stimulation is an operant behavior whereby animals are conditioned to press a lever in order to receive an electrical stimulation of their dopamine neurons. This paradigm is thought to stimulate brain reward pathways and, as such, has been used to clarify the role of dopamine in reward. Striatal extracellular dopamine concentrations were monitored during the acquisition and maintenance of self-stimulation and compared to dopamine release generated by experimenter-delivered and yoked stimulation. Fast-scan cyclic voltammetry in conjunction with carbon-fiber microelectrodes was used to monitor evoked dopamine release in the caudate-putamen during electrical stimulation of the substantia nigra/ventral tegmental area. The sub-second temporal resolution of fast-scan cyclic voltammetry coupled with the micron spatial resolution of the microelectrodes allowed for the measurement of dopamine neurotransmission in real-time. Single experimenter-delivered stimulations, identical to those used during self-stimulation, evoked dopamine release in the caudate-putamen both before and after the self-stimulation sessions. Likewise, yoked stimulations of the substantia nigra/ventral tegmental area delivered to animals untrained to perform self-stimulation resulted in an increase in extracellular dopamine levels. During training sessions, experimenter-delivered stimulations evoked dopamine release. However, as the animals began lever-pressing, extracellular dopamine levels subsequently declined. Taken together, these results suggest that dopamine functions as an alerting device, wherein increases in extracellular dopamine are obtained by unpredicted or novel rewarding stimuli, but not by those which can be anticipated.