The paper presents the results of the study of decaying neon plasma by the method of kinetic spectroscopy. Experimental conditions: neon pressure 0.2–152 Torr, electron density in the initial stage of decay [e] ≤ 5 × 1010 cm-3. The plasma was created by a pulsed barrier discharge with electrodes on the outer surface of a cylindrical glass tube. Discharge frequency 40–160 Hz. On the basis of a comparative analysis of the dependences of the intensities of spectral lines on the time and temperature of electrons in the afterglow, it was shown that in terms of the mechanisms of population, the levels of 2p54p are clearly divided into two groups. Lower levels: from 3p10 to 3p3 (Paschen notation) are associated with the dissociative recombination of molecular ions with electrons and, up to pressures of 0.6 Torr, the lines emitted by them behave identically to the lines of 2p53s ← 2p53p and 2p53p ← 2p53d transitions. The behavior of the upper levels (3p5, 3p2, 3p4, and 3p1) was more complex, and at low pressures, the populations of all 2p54p levels turned out to be related to the impact-radiation recombination of Ne + ions. Significant differences in the dependences of the relative populations of 3d and 4p levels on the neon pressure are discussed.