The T-shaped NeI2(E0(g)(+)) van der Waals (vdW) complexes populated in the NeI2(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 NeI2(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 NeI2(E,v(E),n(E)) complex depends on the v(E) value: it is equal to 8 ns for the NeI2(E,v(E) = 0, n(E)) when vibrational predissociation (VP) is impossible and <= 2 ns when VP channels are open. (C) 2018 Elsevier B.V. All rights reserved.