Gold nanodendrites (GDs) are successfully fabricated via a simple electrochemical method (ECM) using micelle templates formed by two surfactants with various amounts of toluene solvent, the primary surfactant being hexadecyltrimethylammonium bromide (CTAB) and the cosurfactant being tetradodecylammonium bromide (TTAB). To investigate the influence of toluene solvent on the GDs, the amount of toluene solvent was varied in the range from 10 to 50 μL. It was found that the shape of particles was changed from sphere to dendritic shape, and the UV-vis optical absorption measurement revealed a pronounced red shift of the surface plasmon resonance (SPR) peak from 525 to 540 nm. The selected-area electron diffraction (SAED) patterns reveal that GDs are single crystalline with lattice constant a = 4.072 Å. The GDs have been determined to be pure gold with a face-centered cubic (fcc) structure.