A Pd/Cr2O3 hybrid catalyst for cyanation reaction of some aryl halides was synthesized and characterized by XRD, SEM/EDS and TEM. The porous structure of the catalyst was also investigated by BET analysis. All XRD characteristic lines were obtained for Cr2O3 and Pd/Cr2O3 hybrid in good agreement with the reference XRD data. It was found that average particle size of Pd/Cr2O3 composite was about 22 nm. The catalytic efficiency of the Pd/Cr2O3-catalyzed cyanation reaction was evaluated for some m- and p-substituted aryl halides. The influence of solvent, reaction time, and base on the activity of the Pd/Cr2O3 catalyst was investigated, and the optimal reaction conditions were systematically obtained. Catalytic investigations showed that Pd/Cr2O3 hybrid can exhibit very good catalytic performance for cyanation reaction of aryl halides with a high yield of around 90%, and retained its catalytic activity throughout successive 5 cycles. Comparative TEM images of Pd/Cr2O3 hybrid catalyst, as-synthesized and after 5th cycle, showed that nano-sized structure of Pd/Cr2O3 catalyst was protected without significant change.