A spectroscopic study of population processes was carried out for states of the neon atom of the 2p53d configuration in the discharge afterglow in helium with a small admixture of neon ([Ne]/[He] ≈ 10–5) at a pressure of 38 Torr. Based on the comparative analysis of time dependences of the spectral line intensities of the Ne I 2p53d → 2p53d and 2p54d → 2p53d transitions and ratio of ion densities [Ne2+ ]/[HeNe+], it has been found that the formation of excited Ne(2p53d) atoms in the afterglow caused by two dissociative recombination processes: HeNe+ + e → Ne(2p53d) + Ne and Ne2+ + e → Ne(2p53d) + Ne. Distributions of population fluxes of the 2p53d levels \(\Gamma _{3{d_t}}^{HeN{e^ + }}\) and \(\Gamma _{3{d_t}}^{Ne_2^ + }\)—were obtained for each of these processes.