NaCl:Mn2+ nanostructures in the Suzuki phase have been studied by fluorescence (emission and excitation) spectroscopy and atomic force microscopy (AFM) as a function of temperature. The “as-grown” samples give rise to two broad emission bands that peak at 508 (green emission) and 610nm (red emission). The excitation spectrum shows peaks at 227nm and 232nm for emission wavelengths at 508nm and 610nm, respectively. When the samples are heated continuously from room temperature up to 220°C, the green emission (associated to the excitation peak at 227nm) disappears at a temperature close to 120°C, whilst only the red emission remains, which is characteristic of manganese ions. AFM images on the (001) surface (freshly cleaved) show several conformations of nanostructures, such as disks of 20–50nm in diameter. Particularly, the images also reveal nanostructures with rectangular shape of ~280×160nm2 and ~6nm height; these are present only in samples with green emission associated to the Suzuki phase. Then, the evidence suggests that this topographic configuration might be related to the interaction with the first neighbors and the next neighbors, according to the configuration that has been suggested for the Suzuki phase.