This topical review presents new trends in emission spectroscopy of solid nitrogen. Developed approach to study of charged centers and their role in radiation-induced phenomena as well as relaxation processes is discussed. The emission spectroscopy elaborated incorporates correlated in real time detection of several relaxation emission—optical photons, electrons and emission of particles. Key details of this approach applied in research of pre-irradiated by electron beam solid nitrogen and nitrogen-helium nanoclusters grown by a gas jet condensation technique are given. New methods—nonstationary luminescence and nonstationary desorption, designed to study ion-electron recombination reactions—are briefly presented. The selected recent results obtained employing this approach and emission spectroscopy techniques to study the charge related phenomena in condensed nitrogen are summarized. Main attention is given to detection of polyatomic ionic centers containing four and three nitrogen atoms: N4+,N3+,N3−. Their part played in radiation-induced phenomena and relaxation processes, in particular desorption, is discussed.