In this paper our recent results of the Suzuki reaction using [Pd(NH 3 ) 4 ] 2+ -modified nanopore silica under solvent-free conditions are described. [Pd(NH 3 ) 4 ] 2+ -modified nanopore silica was prepared by impregnation using an aqueous solution of [Pd(NH 3 ) 4 ]Cl 2 in water or in acetonitrile. The BET surface area, BJH mean pore diameter and pore volume are 138.8m 2 /g, 8.7nm, and 0.34cm 3 /g, respectively, and the pore size distribution shows a single peak at around 5nm in diameter. It has been shown that the Suzuki reaction is performed in excellent yield by using Pd-modified nanopore silica under solvent-free conditions heated at 90–100°C for 3–5h. It has been found that aryl bromides can be coupled with aryl boronic acids in excellent yield under solvent-free condition. Phenyl iodide was also coupled with phenyl boronic acids in excellent yield, whereas phenyl chloride gave product in poor yield. And KF, CsF or Bu 4 NF were also found to be a convenient base additive.