We have developed an efficient method to generate highly active Pd nanoparticles supported on graphene (Pd/G) by microwave-assisted chemical reduction of the corresponding aqueous mixture of a palladium salt and dispersed graphite oxide (GO) sheets. The Pd/G demonstrated excellent catalytic activity for the carbon–carbon cross-coupling reactions (Suzuki, and Heck) with a broad range of utility under ligand-free ambient conditions in an environmentally friendly solvent system. It also offers a remarkable turnover frequency (108,000h−1) observed in the microwave-assisted Suzuki cross-coupling reactions with easy removal from the reaction mixture, recyclability with no loss of activity, and significantly better performance than the well-known commercial Pd/C catalyst. The catalyst was fully characterized by a variety of spectroscopic techniques including X-ray diffraction (XRD), Raman, TGA, electron microscopy (SEM, TEM), and X-ray photoelectron spectroscopy (XPS). The remarkable reactivity of the Pd/G catalyst toward Suzuki cross-coupling reactions is attributed to the high degree of the dispersion and concentration of Pd(0) nanoparticles supported on graphene sheets with small particle size of 7–9nm due to an efficient microwave-assisted reduction method.