The NAD(P)H-mediated growth of Au nanoparticles (NPs) in the presence of ascorbic acid, AuCl4-, and cetyltrimethylammonium bromide leads to the formation of shaped NP structures consisting of dipods, tripods, and tetrapods. The shaped particles exhibit a red-shifted plasmon absorbance at lambda = 680 nm, consistent with the existence of a longitudinal plasmon exciton. High-resolution transmission electron microscopy analysis of the tripod and tetrapod structures reveals directional growth along the <211> and <010> directions, respectively. The shaped Au NPs could be generated by a biocatalytic process using alcohol dehydrogenase, NAD+, and ethanol, and the resulting blue color provides a colorimetric test for ethanol.