Nanoelectrode and its array in electrochemical applications can provide greater advantages such as fast response times, enhanced mass transport and sensitivities compared with its corresponding planar or micro-electrodes. Unlike the planar of micro-electrodes, nanoelectrode arrays (NEAs) are affected by the dominance of radial diffusion and can result in faster mass transport, which enable to decrease the charging currents and deleterious effects of solution resistance. As a sensor, both the sensitivity and selectivity can be improved in NEAs to yield enhanced nanoscale electrochemical measurement. Thus, the fabrication of NEAs has attracted increasing attention, and has been developed by applying various techniques. In this work, the gold nanoelectrodes coated with vertically-oriented cylindrical nanopores are fabricated for the sake of electrochemical dopamine sensing. The structure of periodic nanoporous membranes was generated by the self-assembly of block copolymers (BCPs). The vertically-oriented cylindrical microdomains were controlled by solvent vapor annealing (SVA). Such nanoporous structure was prepared by degrading the sacrificial blocks of BCPs for instance polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA), polystyrene-block-poly(ethylene oxide) (PS-b-PEO), and polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP). The NEAs indicate the effects of thickness of films, scan rate, pH of electrolytes, and concentration of diffusion species. The morphologies of membranes were characterized by AFM and SEM, and the electrochemical analysis of NEAs from nanoporous membranes was optimized by cyclic voltammetry (CV) measurements. Electrochemical techniques in terms of BCP thin films offer simplicity, rapidity, relative low-cost, and high-sensitivity.