In this publication, a copper acetate-mediated rhodanine polymerization reaction is examined. It is demonstrated that at room temperature, Cu(II) acetate complexes with rhodanine generate solid nanospheres, which, upon heating in a microwave, results in polyrhodanine core-shell nano- and microsphere particles. The structural analysis of the polyrhodanine nanosphere produced by this efficient microwave-initiated method was conducted by Fourier transform infrared spectroscopy, UV-vis spectroscopy, scanning electron microscopy, and transmission electron microscopy. In addition, it is verified that this template-free, efficient, and versatile synthesis of polyrhodanine nanospheres can also be accomplished by introducing a strong oxidant KMnO4 as a cocatalyst with copper acetate without compromising the morphology of the resulting core-shell nanospheres. It is also demonstrated that the polyrhodanine nanospheres can be used to adsorb methyl orange dye, a known contaminant in industrial wastewater.