Spectroscopic methods such as UV–Vis, Raman, ESR and electron spin echo were applied for characterization of polysulfide chromophore thermally formed in cancrinite and zeolite L containing ε-cages in their structures. The UV–Vis and Raman spectra indicated predominant contribution of oligosulfides S n (with n = 2–4) in samples prepared at 650 °C from mixtures of medium alkalinity. Estimated number of S 3 - (blue chromophore) was two orders of magnitude lower (∼3 × 10 16 radicals/g) than in pigments with sodalite or zeolite A structures where it is located in β-cages. The number of S 2 - (yellow chromophore) was even smaller. The continuous ESR and pulse ESR measurements at room temperature and at 10 K indicated that most (>90%) of S 3 - radicals are localized inside ε-cages and remaining ones exhibit free reorientations. The localization in the ε-cages well explains a shift of ESR g-factors compared to that observed for radicals localized in β-cages as well as different dynamical behavior of radical molecules i.e. reorientations around c-axis instead of spatial reorientations existing in β-cages at room temperature.