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The decay dynamics of the α-group ( 2D →4S transition) of N atoms stabilized in the collection of N2–Ne nanoclusters were studied at a temperature of 1.3 K. The variation of the N2/Ne ratio in nanoclusters results in substantial changes in the luminescence spectra of the α-group and in the characteristic decay times for the components of these spectra. In all obtained α-group spectra, the narrow component at λ = 519.9 nm was observed. The spectroscopic results provide information about the structure of the nitrogen–neon nanoclusters. At elevated temperatures ( ≈ 15–36 K), enhanced oxygen β-group luminescence is observed in N2–Ne nanoclusters, with a smaller intensity enhancement than those observed within pure N2 and mixed N2–Kr nanoclusters. These results confirm the energy transfer mechanism, in which excited nitrogen molecules formed on the nanocluster surface transfer energy to the stabilized oxygen atoms through the chain of N2 molecules in a solid matrix.