Hydrogenation of polymer having C C double bond can be carried out with the metal-organic complex as catalyst, which has the property of themoregulated phase transfer. In this study, a new complex RhCl[PPh[(OCH(2)CH(2))(5 <= n <= 6)CH(3)](2)](3) (Rh/AEOPP) was synthesized with a good yield, which was further used as catalyst to selectively hydrogenated nitrile-butadiene rubber (HNBR). This is the first time that Rh/AEOPP complex was synthesized and applied in nitrile-butadiene rubber (NBR) hydrogenation. The result shows that hydrogenation degree of product (HNBR) can be extended to 90%, when the condition is [Cat] = 3% (based the weight of NBR), L(2): Cat (Weight Ratio) = 2, [NBR] = 5% (based on the weight of xylene solution), P (H(2)) = 1.5 MPa, T = 155 degrees C, and t = 8 h. Also, by adjusting temperature, the catalyst could be easily separated from products with 89% catalyst complex recovery. In addition, (1)H-NMR and infrared (IR) spectra showed that C=C double bonds in NBR was successfully hydrogenated without causing reduction of the CN group. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 123: 1040-1046, 2012