The T-shaped NeI ₂(E0 _g ⁺) van der Waals (vdW) complexes populated in the NeI ₂(E,v _E = 0–2, n _E=0–2 ← B,19,n _B = 0 ← X,0,n _X = 0) excitation pathway have been studied. Analysis of the luminescence excitation spectra, luminescence spectra themselves and temporal behaviors of the luminescence intensities of the transitions observed has been carried out. The NeI ₂(E,v _E,n _E) luminescence has been discovered. This is the first direct observation of a halogen molecule vdW complex luminescence. It has also been found that lifetime of the NeI ₂(E,v _E,n _E) complex depends on the v _E value: it is equal to 8 ns for the NeI ₂(E,v _E = 0,n _E) when vibrational predissociation (VP) is impossible and ≤2 ns when VP channels are open.