Highly boron-doped diamond thin-film electrodes were examined for various possible applications in electroanalysis. Electrochemical oxidation of dopamine and NADH was investigated using cyclic voltammetry and chronoamperometry. Comparison experiments were performed using glassy carbon electrodes. Anodically treated diamond electrodes made it possible to determine dopamine selectively with high sensitivity in the presence of a large excess of ascorbic acid in acidic media. A detection limit of 50 nM was obtained using chronoamperometry. The treated electrodes were found to be stable for several months. Electrochemical oxidation of NADH was carried out at as-deposited diamond electrodes, with which very stable and reproducible cyclic voltammograms for NADH oxidation were obtained, unlike glassy carbon, at which a significant positive shift (similar to 200 mV) in the peak potential was observed within 1 h. The amperometric detection limit was found to be similar to 10 nM. Interference of ascorbic acid was minimal using untreated electrodes when the concentration of ascorbic acid was comparable to the NADH concentration. Diamond microelectrodes small enough to consist of only one or two high quality microcrystals were fabricated in order to compare the electrochemical behavior with that of polycrystalline thin film electrodes, which contain large numbers of grain boundaries, at which non-diamond (sp(2)) carbon can exist. This work demonstrates the potential of diamond electrodes for electroanalytical applications.