Prussian blue (PB) modified nanoporous gold (NPG) electrodes exhibit great potential for improving the detection sensitivity and stability for hydrogen peroxide monitoring. The NPG provides large surface-to-volume ratio as well as diffusion 'highways' to assist the transfer of the ions. In the present work, we optimized the deposition time for NPG fabrication and examine the electrochemical performance of the electrodes. A critical deposition time on the electrochemical performances including linear range, operational stability and sensitivity was experimentally determined. Below and above such a deposition time, two different growth patterns of the microstructures were observed. This transition of deposited structures corresponding to the critical time results in different pathways for electron transfer and ion diffusivity through PB lattice.