Microelectrodes are typically used for neurotransmitter detection, but nanoelectrodes are not because there is a trade-off between spatial resolution and sensitivity, which is dependent on surface area. Cavity carbon nanopipette electrodes (CNPEs), with tip diameters of a few hundred nanometers, have been developed for nano-scale electrochemistry. Here, we characterize the electrochemical performance of CNPEs with fast-scan cyclic voltammetry (FSCV) for the first time. Dopamine detection is compared at cavity CNPEs, with a depth equivalent to a few radii, and open-tube CNPEs, an essentially infinite geometry. Open-tube CNPEs have very slow temporal response that changes over time as the liquid rises in the pipette. However, the cavity CNPEs have a fast temporal response to a bolus of dopamine that is not different than traditional carbon-fiber microelectrodes. Cavity CNPEs, with a tip diameter of 200-400 nm, have high currents because the small cavity traps and increases the local dopamine concentration. The trapping also leads to a FSCV frequency independent response and the appearance of cyclization peaks that are normally observed only with large concentrations of dopamine. CNPEs have high dopamine selectivity over ascorbic acid (AA) due to the repulsion of AA by the negative electric field at the holding potential and the irreversible redox reaction. In mouse brain slices, cavity CNPEs detected exogenously-applied dopamine, showing they do not clog in tissue. Thus, cavity CNPEs are promising neurochemical sensors that provide spatial resolution on the scale of hundreds of nanometers, useful for small model organisms or locating near specific cells.