Abstract: An exploratory experiment on Multi-Nucleon Transfer (MNT) reactions was successfully conducted at the FRS Ion Catcher setup at GSI. The experiment demonstrated the production of MNT-driven radioactive ion beams (RIBs) produced by decelerated relativistic beams. A beam of 238U ions was reacted with a 209Bi target at near-Coulomb barrier energies inside the specially modified Cryogenic Stopping Cell (CSC) for the production and thermalization of MNT products. These products were then identified using a Multiple-Reflection Time-Of-Flight Mass Spectrometer (MRTOF-MS). The observation of target-like MNT fragments along the A = 211 isobaric chain provided a proof-of-principle for future MNT studies with the FRS Ion Catcher setup.