Hierarchical leaf-like gold nanolayers were electrodeposited using choline chloride as a shape directing agent and characterized using field emission scanning electron microscopy. The electrooxidation behavior of vorinostat was then studied on the nanolayers and the kinetic parameters of the electrodic process were obtained by voltammetric measurements in a phosphate buffer solution at pH 7.40. Vorinostat was electrooxidized on the nanolayers’ surface at a lower potential and with a higher rate, compared to a polycrystalline smooth gold surface, through an irreversible process. Based on the results, an amperometric sensor was designed using the hierarchical leaf-like gold nanolayers for the determination of vorinostat. A linear dynamic range of 4.0–52μmol L−1 with a calibration sensitivity of 7.7mAmol−1L, and a detection limit of 1.40μmolL−1 were obtained. The amperometry method was also applied to the analysis of vorinostat capsules.