A fast, simple and sensitive electrochemical method for sensing peroxide-based explosives based on their acid treatment is reported. The method relies on the high electrocatalytic activity of Prussian-blue (PB)-modified electrodes towards the acid-generated hydrogen peroxide in the harsh acidic medium (down to pH 0.3) used for releasing hydrogen peroxide. Such effective operation of PB electrochemical sensors in strongly acidic media eliminates the need for an additional neutralization step required in analogous peroxidase-based assays (due to acid-induced enzyme deactivation processes). Factors affecting the efficiency of the acid pre-treatment of triacetone triperoxide (TATP) have been examined and optimized to allow its sensitive measurement down to the 50 ng level within 60 s. Chronoamperometric detection of microgram amounts of solid TATP, following a one-minute acid mixing and placing a 20 μL droplet onto a disposable PB-modified screen-printed electrode is illustrated. Similar results were obtained for the peroxide explosive hexamethylene triperoxide diamine (HMTD). By greatly simplifying the analytical procedure, such an acid-operated ‘artificial peroxidase’ electrocatalytic transducer holds great promise for designing ‘one-step’, user-friendly, miniaturized, cost-effective devices for field screening of peroxide explosives.