The spectroscopic study of population processes of neon 2p ⁵5s states was carried out in helium afterglow with small admixture of neon at PHe = 38.1 torr, [He]/[Ne]=10^-5 with pulsed discharge afterglow in helium with small admixture of neon (pressure equal to 38.1 mm Hg;). It is established that the main mechanism of population of 3s ₂ level (in Paschen's notation) in the discharge and the initial after-glow is the excitation transfer from metastable atoms of He(2¹ S ₀). The other three levels - 3s ₃, 3s ₄, and 3s ₅ - corresponding to 2p ⁵5s configuration are populated in the afterglow as a result of the dissociative recombination HeNe⁺ of ions with electrons. The same process is also the main channel of population of 3s ₂ level in the late afterglow phase, when the concentration of He(2¹ S ₀) atoms is small. The hypothesis of recombination mechanism is confirmed by observation of the response of line intensities to pulsed electron heating. The partial coefficients of dissociative recombination into 2p ⁵5s states are estimated.