This paper reviews optical diagnostic methods and approaches applied to study the fundamentals of streamer discharges, considering the peculiarities of streamers developing in atmospheric gases at high (1 bar) as well as low (< 10 mbar) pressures. A critical discussion is devoted to the cross-sections for electron-impact excitation/ionization/dissociation processes and corresponding rate constants in relation to methods used to probe streamer properties. The most important spectrometric signatures of radiative transitions of diatomic as well as atomic species are discussed on the basis of their synthetic models with a brief guide on how to simulate the most important emissions. Basic differences between UV–vis–NIR spectra produced by electron-impact and various heavy-particle energy-transfer processes during streamer evolution are presented and possible strategies based on 2D projections of cylindrically symmetric streamers to determine radial distributions of excited species within the streamer channel are discussed. The use of emission techniques to obtain the rotational temperatures and vibrational distributions of excited states of diatomics and laser-induced fluorescence techniques to probe the vibrational manifold of the lowest triplet metastable state of the nitrogen molecule is addressed.