In this study, vitamin B12 (VB12) modified with a (3-glycidyloxypropyl)trimethoxysilane (GMSI) moiety grafted onto KCC-1 (KCC-1/GMSI/VB12) was prepared for the first time. Its capability was evaluated for the carbonylative Suzuki–Miyaura crosscoupling reaction between carbon monoxide, 4-iodoanisole and phenylboronic acid, affording the desired products in high yield. Applying 1 mg of catalyst and 1 mmol of K₂CO₃ as base in 10 mL anisole and heating under reflux for 1 h are the best conditions for the reaction. The catalysts were very active in catalytic recycling experiments over ten catalytic cycles.