A new method for the repetitive batch silylative coupling (trans-silylation) of vinylsilanes with vinyl boronates in the presence of Ru(CO)Cl(H)(PCy 3 ) 2 immobilized in poly-(ethylene glycols) (PEGs) has been developed. Three PEGs (PEG600, PEG2000, and MPEG2000) with different molecular weights and end groups (MW = 600−2000) were tested as solvents and immobilization media, while an aliphatic solvent (n-hexane or n-heptane) or supercritical CO 2 was used for product extraction. By applying 2 mol % of the Ru−H catalyst, it was possible to carry out up to 15 complete runs, with the predominant formation of 1-boryl-1-silylethenes. This immobilization strategy permitted for catalyst reuse and obtaining higher TON values (approximately 660−734) compared to the reaction in conventional solvents (∼50). Detailed kinetic studies of the most effective catalytic system were performed to determine catalyst activity and stability. Moreover, the reactions were carried out in an MPEG2000/scCO 2 biphasic system, positively influencing the process sustainability.