Abstract The T -shaped HeI 2 ( E 0 g + ) van der Waals complexes populated in the HeI 2 ( E , v E = 0–2, n E = 0 ← B ,19, n B = 0 ← X ,0, n X ) excitation pathway have been studied. Analysis of the luminescence excitation spectra as well as the I 2 ( E 0 g + → B 0 u + , D 0 u + → X 0 g + , and D ′2 g → A ′2 u ) luminescence spectra themselves has been carried out. It has been shown that the I 2 ( D → X , and D ′ → A ′) luminescence is due to HeI 2 ( E ← B ) transitions with subsequent electronic predissociation. We have determined dissociation energies of the HeI 2 ( E , v E = 0–2) complexes, vibrational populations of the E , D states and branching ratios of vibrational and electronic predissociations. One can suppose that luminescence of the HeI 2 ( E , v E = 0, n E = 0) complexes occurs.