The first synthesis of porous, optically active, magnetic Fe3O4@poly(N-acryloyl-leucine) inverse core/shell composite microspheres is reported, in which the core is constructed of chiral polymer and the shell is constructed of Fe3O4 NPs. The microspheres integrate three significant concepts, “porosity”, “chirality”, and “magneticity”, in one single microspheric entity. The microspheres consist of Fe3O4 nanoparticles and porous optically active microspheres, and thus combine the advantages of both magnetic nanoparticles and porous optically active microspheres. The pore size and specific surface area of the microspheres are characterized by N2 adsorption, from which it is found that the composite microspheres possess a desirable porous structure. Circular dichroism and UV-vis absorption spectroscopy measurements demonstrate that the microspheres exhibit the expected optical activity. The microspheres also have high saturation magnetization of 14.7 emu g–1 and rapid magnetic responsivity. After further optimization, these novel microspheres may potentially find applications in areas such as asymmetric catalysis, chiral adsorption, etc.