Four main types of signals have been fixed in the EPR-spectra of the studied perlites: structural Fe3+ with g = 4.3, iron-bearing microphases with a. broad signal at 8 = 3.2–2.1, Mn2+ with a six-component signal and a sensitive to irradiation electron center of the E1’ type with g = 1.999. Combinations of two or more of the above mentioned centers have been presented. Dependences have been established between the different colour varieties of perlites and the type and concentration of electron-hole defects: for Fe3+ high values have been obtained for the pale-coloured varieties and low values for the dark varieties with an absence among the reddish brown varieties; Mn2+ has been characteristic for some of the pale-coloured varieties and the radiation sensitive center has been observed in the reddish brown varieties. The content of magnetoconcentrated iron microphases does not influence the colour of the perlites.