A facile aerosol-based process (ABP) is developed to vary the placement of iron nanoparticles on the external surface of carbon microspheres or within the interior. This is accomplished through the competitive mechanisms of sucrose carbonization and the precipitation of soluble iron salts, in an aerosol droplet passing through a high temperature heating zone. At lower aerosolization temperatures, carbonization occurs first leading to iron salt precipitation on the external surface, while at higher temperatures interior placement occurs through concurrent iron salt precipitation and sucrose carbonization. The resulting composites are highly conducive to the reductive dechlorination of compounds such as trichloroethylene (TCE) as the carbon support is a strong adsorbent, and zerovalent iron effectively reduces TCE to innocuous gases such as ethane. Since both iron and carbon are widely used catalysts and catalyst supports, the simple process of modifying iron placement has significant potential applications in heterogeneous catalysis.