In this work, the aqueous speciation of Rh(III) in chloride medium was investigated by UV-vis spectroscopy for ligand to metal ratios R = (Cl-)/(Rh) ranging from 300 to 5000, at fixed Rh concentration (2.4 × 10-3 M). Under the chemical conditions of this work, no time evolution was observed, which allows for the fitting of the UV-vis data by Principal Component Analysis (PCA) and Multi-Curve Resolution (MCR). From this, and by comparison with literature data, the three independent species [RhCl₄]-, [RhCl₅]2- and [RhCl₆]3- were identified, their individual absorption spectra derived and their respective contribution to the collected experimental UV-vis spectra calculated. Then, extraction of Rh(III) towards the ionic liquid trihexyltetradecylphosphonium chloride was performed. Comparison with the speciation data gives insight into the extraction mechanism and the extracted species.