Highly cross-linked imidazolium-based materials,obtained by radical oligomerization of bisvinylimidazolium\ud salts in the presence of 3-mercaptopropyl-modified silica gel, were used as supports for palladium catalysts. Thanks to the high imidazolium loading these materials were able to support a high amount of the metal (10 wt%). Such materials\ud were characterized by several techniques (13C magic angle spinning nuclear magnetic resonance, the Brunauer–\ud Emmett–Teller technique, X-ray photoelectron spectroscopy, and transmission electron microscopy).\ud The palladium catalysts displayed good activity allowing the synthesis of several biphenyl compounds\ud in high yields working with only 0.1 mol% of palladium loading at 50 8C in ethanol/water under batch condition. Moreover, a flow apparatus, to optimize\ud the efficiency of the isolation of the pure products and minimize waste (E-factor), was investigated.\ud For the first time the palladium catalyst and base(K2CO3) were placed in two separate columns allowing an easy recovery of the products with very low\ud E-factor values (<4). Waste production was reduced by over 99% compared to classic batch conditions.\ud Because of the high Pd loading only 42 mg of catalysts were employed in the Suzuki reaction between 160 mmol of 4-bromotoluene and 180 mmol of phenylboronic acid. No loss in activity was observed

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3-Mercaptopropyl-modified silica-supported bis-imidazolium Pd-catalysts are developed and successfully utilized for Suzuki reactions. The procedures are either performed as batch reactions or in a continuous-flow mode. -(PAVIA, C.; BALLERINI, E.; BIVONA, L. A.; GIACALONE, F.; APRILE, C.; VACCARO, L.; GRUTTADAURIA*, M.; Adv. Synth. Catal. 355 (