Constant potential amperometry with Nafion-coated carbon-fiber electrodes has been evaluated as a technique for in vivo detection of the neurotransmitter dopamine. The results of this technique have been compared to results obtained with fast-scan cyclic voltammetry at the same electrode during release of dopamine into the extracellular space of the brain during electrical stimulation of neurons. The data indicate that constant potential amperometry is a viable technique for detecting low concentrations of dopamine. Dopamine permeates the film more quickly with constant-potential amperometry than with repeated fast-scan cyclic voltammetry as predicted by diffusion equations. For the case of cyclic voltammetry, it is demonstrated that the temporal delay caused by diffusion through Nafion film can be removed by deconvolution procedures. Despite the suitability of constant potential amperometry as an in vivo monitoring technique, it does have several disadvantages when compared to fast-scan cyclic voltammetry. The diffusion layer extends outside of the Nafion film making determination of concentration based on in vitro calibrations more difficult to interpret. The reported concentrations are larger than obtained by cyclic voltammetry, a technique with the diffusion layer restricted to the Nafion film, and this result is likely an underestimation of the effect of the catalytic reaction between the o-quinone of dopamine and ascorbate. Amperometry was found to provide only slightly improved signal-to-noise ratios than cyclic voltammetry despite the use of greater filtering. This was because the advantage of dopamine accumulation in the film was lost. In addition, the small magnitude of the amperometric signal makes it more susceptible to electrical interference.