This study investigates four phenothiazinium dyes including methylene blue (MB) and three analogues containing auxochrome variation 2–4 as oxygen colorimetric indicators prepared by their incorporation into two types of oxygen permeable materials containing: a) polyvinyl alcohol substrate with additional TiO2 photocatalysts (PhOxIn), and b) carboxymethylcellulose polymer matrix containing glucose and KOH (ChOxIn). In vacuum packages where volumetric concentrations of oxygen were below 0.01 %, the leuco forms of the tested phenothiazinum dyes were readily oxidised, initiating the colour turn from white to blue. The redox processes involved were explored by experimental electron paramagnetic resonance EPR and UV–vis spectroscopic methods and further supported by theoretical quantum chemistry. The EPR experiments showed that the chemical oxidation of the leuco-form of the phenothiazinium dyes 1–4 produced transient aminyl radical species with the single electron mainly located at the nitrogen atom of the heterocyclic core. The formation of these transient aminyl species was also perceived by UV–vis spectroscopy, their absorption maxima situated in the 552–592 nm range being also supported by TD-DFT theoretical calculations.