Carbon dioxide-expanded methanol (CXM) is for the first time employed to recover Wilkinson's catalyst from the matrix of hydrogenated nitrile butadiene rubber (HNBR) using the chelating agent N,N,N',N',N ''-pentamethyldiethylenetriamine (PMDETA). The effects of temperature and pressure on the extraction performance were carefully investigated over the temperature range of 40-100 degrees C and the pressure range of 20-20 MPa. Increasing temperature effectively increased the extraction rate and became less influential when temperature is above 80 degrees C. Increasing pressure over the different pressure ranges at 80 degrees C impacted the extraction rate differently. 6 MPa was considered as the optimal pressure at 80 degrees C. The rhodium residue was reduced from 700 to 222 ppm by a 5 h extraction at 6 MPa and 80 degrees C. An extraction mechanism was illustrated for interpreting the present extraction system and guiding the future work. This study establishes a technology platform for separating the expensive catalyst from the polymer matrix, using "green" CO2-expanded liquids. (C) 2012 Elsevier B.V. All rights reserved.