Fast ion physics is an active field of research in the fusion community, but most studies focus on deuterium fast ions. The generation and investigation of energetic helium in present devices, however, provide significantly more insight on how the fast alpha particles produced from fusion reactions, will behave in future reactor plasmas. Fast helium ion populations can be measured with charge exchange recombination spectroscopy (CXRS) in the wings of the helium spectral line (He IIn = 4–3, 468.6 nm) providing information on their distribution function. CXRS measurements of energetic 3He ions, a first for ASDEX Upgrade, are presented. The 3He ions are accelerated to high energies by a three-ion cyclotron resonance frequency (ICRF) heating scenario in a mixed hydrogen–deuterium plasma. The spectral signature of the energetic helium ions in the charge exchange spectra is presented and compared with the theoretical predictions obtained with the TORIC-SSFPQL code. The magnitude of the predicted charge exchange spectral radiance, obtained via forward-modelling of the spectrum utilising TORIC-SSFPQL distribution functions, and the expected energies of the ions agree well with the measurement, confirming that the spectral feature is due to ICRF-accelerated 3He ions. Comparisons between the experimental measurement and the modelling reveal discrepancies that illuminate details of the velocity distribution function of these ions.