Ion accelerators have a fundamental role in atomic and nuclear studies as well as in applied physics, including the modification and characterization of materials. The precise knowledge of the energy of accelerated ions is of utmost importance, especially for cross-section measurements or for accurate depth profiling using narrow resonances. The 3 MV Cockcroft–Walton tandem accelerator of IFIN-HH from HVEC was installed in 2012. The machine is mainly dedicated to ion beam analysis, ion implantation, and astrophysics studies at low energy. In this work, we report on the first calibration for alpha particles of the terminal voltage using a technique based on Rutherford backscattering spectrometry measurements. The energies of the α particles from a mixed spectroscopic 239Pu + 241Am α source are compared with the energies of 4He projectiles backscattered into a silicon detector by carbon and gold layers. The position of the 16O(α,α) 16O resonance around 3.038 MeV at backscattering angles of 145° and 165° was remeasured. Our results are compared with recent results reported in the literature.