In March 2023, the first rare isotope beam (RIB) was successfully extracted from the Isotope Separation On-Line (ISOL) at the RAON heavy-ion accelerator facility. Surface-ionized beams of lithium (Li), sodium (Na), and aluminum (Al), produced by bombarding a silicon carbide (SiC) target with a 70 MeV proton beam, were delivered to the RIB separation and transport system. The production efficiency of Na isotopes from the SiC target was generally satisfactory, and a short-lived isotope, 24mNa (t1/2 = 20 ms), was successfully measured. The performance of the ISOL RIB separation and transport system was validated through on-line experiments with both stable and radioactive sodium beams. The preparation of highly charged ions, meeting the injection requirements for the SCL3 post-accelerator (energies of 10 keV/u and an A/q ratio of < 6), was achieved using the Electron Beam Ion Source (EBIS). The ISOL RIB, 25Na5+, was successfully charge-bred and transported to the post-accelerator. This presentation will discuss the production, charge breeding, and post-acceleration of RAON's first RI beam.