The valence band electronic structure of isolated silver iodide nanoparticles (AgI NP) was investigated by vacuum‐ultraviolet aerosol photoelectron spectroscopy using the velocity map imaging technique (VUV VMI‐PES). The VUV VMI‐PES results were obtained for polydisperse aerosol produced by aggregation of hydrocolloid of silver iodide particles 8 ‐ 15 nm in size. The ionization energy of the AgI particles was found to be 6.0 ± 0.1 eV with respect to the vacuum level. The DFT calculations showed that the main contribution to the density of AgI electronic states in the valence region originates from I 5p orbitals. The dependence of the asymmetry parameter on the electron energy showed that the value of the characteristic energy loss of excited photoelectrons was 2.7 eV, which coincided with the band gap of the nanomaterial.