The existence of a population of ions, with energies well above the corresponding thermal values, in plasmas heated by neutral beam injection (NBI) in the stellarator TJ-II and in other magnetically confined plasmas devices is well known. Moreover, during the NBI phase of the TJ-II, edge-localized mode-like (ELM-like) instabilities often appear. This work studies the relationship between fast ions escaping from TJ-II plasmas and such ELM-like events. For this, an ion luminescent probe (LP), operated with a fast scintillator (decay time = 27 ns) and high-speed conditioning electronics (100 MHz), is used to measure, without pile-up effects, the energy distribution of suprathermal ions across the energy range, from 1 to 30 keV. It is found that the LP detects suprathermal ion populations that can be related to ELM-like events whose temperatures oscillate between 0.5 and 3 keV and that can be distinguished in a spectrogram of the LP response as an increase in frequencies from 15 to 150 kHz. Finally, observations of substructures within ELM-likes events, consisting of bursts of ions, with times between 5 and 15 μs are also reported. Such substructures have been observed previously in both tokamaks and stellarators in ion saturation current, high-speed camera images, etc. However, understanding the fast-ion component can provide new and relevant information about the behaviour of ions.