Suzuki-Miyaura coupling reaction is one of the most versatile and utilized reactions for the selective construction of C-C bonds, in particular for the formation of biaryl derivatives. There have been a number of protocols to achieve an efficient Suzuki-Miyaura coupling reaction, although the utilization of expensive bases, solvents, scarce or difficult handling phoshine ligands made the reaction not practical. We developed a mild and efficient protocol for the phosphine-free Suzuki-Miyaura coupling reaction catalyzed by Pd/C at room temperature in an aqueous and/or alcoholic solvent (Scheme 1). This procedure features inexpensive reagents, solvents with low toxicity and extremely mild reaction conditions. Furthermore, Pd/C is reusable without significant alteration of the yields of the cross-coupled product. The present method is applicable to the synthesis of heterocyclic biaryl derivatives, and alkenyl boronic acids and can also be used boronic acid esters as a coupling partner (Scheme 2).