Groundwater is an extremely important resource that may, however, contain a variety of toxic and bioaccumulative contaminants. Traditional “Pump and Treat” technologies for treating contaminated groundwater are no longer time- or cost-effective; therefore, new technologies are needed. In this work, we synthesized core–shell materials of micrometric dimensions based on the interaction of iron particles (the core) and fermentable biopolymers such as polyhydroxybutyrate (PHB, the surrounding shell) to be used in permeable reactive barriers for the removal of chlorinated pollutants from contaminated groundwater. The materials were prepared by precipitation techniques that allowed stable preparations to be obtained, whose chemico-physical properties were thoroughly characterized by scanning electron microscopy, porosimetry, Fourier transform infrared spectroscopy (FTIR), thermogravimetric analyses, disc centrifuge analysis, and dynamic light scattering. The properties of the prepared materials are very promising, and may enhance the performance of permeable reactive barriers towards chlorinated compounds.