A pyrogallol (PG) and formaldehyde condensation reaction was carried out under alkaline conditions to prepare the pyrogallol formaldehyde resol resin (PGNR). Polymerization was performed to establish the nano resin formation. Obtained nano resin was used as an adsorbent for recovery of rhodium(III) ions from chloride-containing solutions. This kind of recovery was very simple and useful for generating little secondary wastes. The interaction of adsorption also was investigated: The proposed adsorption of the aquachlororhodium(III) species mostly takes place via a ligand exchange mechanism. PGNR and Rh-adsorbed PGNR were characterized by scanning electron microscopy, energy-dispersive spectrometry, X-ray diffraction spectroscopy, and Fourier transform infrared-attenuated total reflection spectroscopy. By utilizing such characteristics of polyphenol resin, PGNR can be applied to recover Rh(III) efficiently and simply with low cost.