A natural phengite-2M1 of composition (K0.95Na0.05)(Al0.76Fe0.14Mg0.10)2(Si3.25Al0.75)O10(OH1.96F0.04) [a = 5.2173(1) Å b = 9.043(2) A, c = 19.989 (1) Å and = 95.734(4)°] was studied using in situ high-temperature FTIR. Correlations to structural changes were made using previously-reported neutron diffraction data from the same sample. Correlations have been made between the microscopic atomic displacements (arising from thermal effects) and analogous macroscopic properties, such as bond strain and ditrigonal distortions. Spectra were collected in the far-infrared region to study the behaviour of the interlayer(K+) cation and also in the mid-infrared region to distinguish the Si–O stretching modes. We found anisotropic thermal expansion of the interlayer site. The K–O bond length is divided into K–Oouter and K–Oinner, and the K–Oinner bond length is correlated with the far-infrared spectra. The thermal dependence of the correlation between K–O bond length and corresponding far-infrared stretching frequency is different from the effect of the chemical composition. We also found that the K–O bond strain could be successfully resolved into the sum of inner strain and lattice strain. The Si–O stretching mode, obtained from the mid-infrared measurements, showed only weak changes. However, the neutron refinement data showed different thermal behaviour for distinct crystallographic T-sites.