Paramagnetic microspheres with core-shell-ed structures were successfully synthesized by electroless plating technique. The surface morphology and core-shell-ed structures of the paramagnetic microspheres were examined by scanning electron microscopy as well as optical microscopy. Under magnetic fields, the core-shell-ed microspheres self-assembled into ordered structures (chains, columns, or three-dimensional ordered structures) because of magnetic dipole-dipole interaction, having potential applications in optics.