The ability to detect traces of highly energetic explosive materials sensitively, selectively, accurately, and rapidly could be of enormous benefit to civilian national security, military applications, and environmental monitoring. Unfortunately, the detection of explosives still poses a largely unmet arduous analytical problem, making their detection an issue of burning immediacy and a massive current challenge in terms of research and development. Although numerous explosive detection approaches have been developed, these methods are usually time-consuming, require bulky equipment, tedious sample preparation, a trained operator, cannot be miniaturized, and lack the ability to perform automated real-time high-throughput analysis, strongly handicapping their mass deployment. Here, we present the first demonstration of the "direct" electrochemical approach for the sensitive, selective, and rapid vapor trace detection of TATP and HMTD, under ambient conditions, unaffected by the presence of oxygen and hydrogen peroxide species, down to concentrations lower than 10 ppb. The method is based on the use of Ag-nanoparticles-decorated carbon microfibers air-collecting electrodes (μCF), which allow for the selective direct detection of the organic peroxide explosives, through opening multiple redox routes, not existent in the undecorated carbon electrodes. Finally, we demonstrate the direct and rapid detection of TATP and HMTD explosive species from real-world air samples.