Transition metal hexacyanoferrates are versatile inorganic compounds widely employed for the assembling of sensors and biosensors in a variety of different electroanaytical applications. A modified version of the recently introduced redox competition mode of scanning electrochemical microscopy (RC-SECM) was exploited to visualize the local electrocatalytic activity of microstructured Prussian blue (PB) films towards the reduction of H2O2 with improved lateral resolution. The PB films were electrochemically deposited in a spot on glassy carbon surfaces using a droplet cell. The influence of the potential applied to the PB modified surface on the current at the SECM tip was evaluated when both the sample and the SECM tip were competing for H2O2 in solution. Thus, high local electrocatalytic activity is indicated by low currents at the SECM tip. The same strategy was successfully employed for the characterization of the performances of a biosensor employing the enzyme glucose oxidase (GOx) immobilized within a polymer hydrogel matrix on the top of PB-modified glassy carbon electrodes.