The minerals of carletonite group, fluorcarletonite, KNa4Ca4[Si8O18](CO3)4(F,OH)·H2O and carletonite, Na4Ca4[Si8O18](CO3)4(OH,F)·H2O, were investigated using a multi-method approach. A detailed comparative chemical study of the minerals was carried out using electron probe microanalysis and Fourier transform infrared spectroscopy. Using X-ray techniques and the results obtained, geometrical and distortion characteristics of the mineral structures are calculated and the successful crystal-structure refinement of these two natural compounds are given. Using spectroscopic and luminescence methods and ab initio calculations, it is shown that hole defects (CO3)•– are responsible for the colouration of the samples studied. Luminescence due to 5d–4f transition in Ce3+ ions is observed in both investigated compounds. Moreover, luminescence attributed to intrinsic luminescence, corresponding to the decay of electronic excitations of (CO3)2– complexes in the carletonite sample, is registered for the first time in phyllosilicates. An analysis of the optical absorption spectra and g-tensor values suggests that (CO3)•– defects in the crystal structure are localised in the C1 positions. Identification of these specific properties for these sheet silicates, with a two-dimensional infinite tetrahedral polymerisation, indicates that carletonites could be prospective materials for novel phosphors and luminophores.