The effects of low-temperature on the crystal structure of a natural epidote [Ca1.925Fe0.745Al2.265Ti0.004 Si3.037O12(OH), a = 8.8924(7), b = 5.6214(3), c = 10.1547(6) angstrom and beta = 115.396(8)degrees at room conditions, Sp. Gr. P2(1)/m] have been investigated with a series of structure refinements down to 100 K on the basis of X-ray single-crystal diffraction data. The reflection conditions confirm that the space group is maintained within the T-range investigated. Structural refinements at all temperatures show the presence of Fe3+ at the octahedral M(3) site only [%Fe(M3) = 70.6(4)% at 295 K]. Only one independent proton site was located and two possible H-bonds occur, with O(10) as donor and O(4) and O(2) as acceptors. The H-bonding scheme is maintained down to 100 K and is supported by single crystal room-T polarised FTIR data. FTIR Spectra over the region 4,000-2,500 cm(-1) are dominated by the presence of a strongly pleochroic absorption feature which can be assigned to protonation of O(10)-O(4). Previously unobserved splitting of this absorption features is consistent with a NNN influence due to the presence of Al and Fe3+ on the nearby M(3) site. An additional relatively minor absorption feature in FTIR spectra can be tentatively assigned to protonation of O(10)-O(2). Low-T does not affect significantly the tetrahedral and octahedral bond distances and angles, even when distances are corrected for "rigid body motions". A more significant effect is observed for the bond distances of the distorted Ca(1)- and Ca(2)-polyhedra, especially when corrected for "non-correlated motion". The main low-T effect is observed on the vibrational regime of the atomic sites, and in particular for the two Ca-sites. A significant reduction of the magnitude of the thermal displacement ellipsoids, with a variation of U-eq (defined as one-third of the trace of the orthogonalised U-ij tensor) by similar to 40% is observed for the Ca-sites between 295 and 100 K. Within the same T-range, the U-eq of the octahedral and oxygen sites decrease similarly by similar to 35%, whereas those of the tetrahedral cations by similar to 22%.