A quick and easy method for the preparation of Pd2+ metal ion substituted in ceria, Pd0.09Ce0.91O2-δ solid solution oxide, is described. The Pd0.09Ce0.91O2-δ solid solution oxide was fully characterized by XRD, ICP-OES, BET, XPS, SEM, EDX, TEM, TGA and Raman spectroscopy. All characterization techniques strongly suggested that Pd2+ was successfully incorporated into the lattice structure of ceria. The effect of the reaction conditions on the catalytic properties of the Pd0.09Ce0.91O2-δ solid solution catalyst initially was studied in detail with the model Heck reaction of iodobenzene and methylacrylate to obtain optimum reaction conditions. The Pd0.09Ce0.91O2-δ solid solution catalyst then afforded substituted alkenes in good to excellent yields under these optimum reaction conditions. Steric and electronic effects were also studied, and were found to influence the catalytic activity. Characterization of the used catalyst suggests that Pd2+ in Pd0.09Ce0.91O2-δ is reduced in situ to Pd0 when employed in the Heck cross-coupling reactions. The catalyst was easily recovered by centrifuge and reused three times without significant loss of catalytic efficiency.