Fourier-transform infrared (FTIR) spectroscopy is a widespread and highly sensitive analytical method for the identification and characterization of a wide range of materials via their infrared (IR) absorption bands. Until now, the potential of IR microspectroscopy and imaging for the characterization of works of art or other objects of cultural heritage significance has been only partially exploited; in particular the use of the synchrotron radiation (SR) IR microprobe to study, at the micron scale, materials of interest for archaeological and cultural heritage studies has become popular only in the past decade. One of the main requirements imposed on the studies of ancient and/or valuable materials is that the techniques applied must be non-destructive. In this scenario, SR-based FTIR methods are perfectly suitable. Moreover, IR spectroscopy and imaging are emerging techniques that combine the assets of IR in terms of molecular specificity with the unique properties of synchrotron light. SR-FTIR micro-spectroscopy offers great advantages over conventional methods because it provides a broader spectrum (down to THz) and higher spectral quality (signal/noise ratio) at the highest spatial resolution (diffraction limited). This is due to the high brilliance and collimation of SR-IR, while still being non-damaging to the investigated system. The unique SR-IR parameters are essential for the compositional analysis of the tiny, sub-millimetric samples characteristic of ancient materials, which are heterogeneous by nature, and with complex molecular distributions at extremely variable concentrations. SR-FTIR spectroscopy and imaging can be applied successfully to the characterization of organic and inorganic materials via so-called IR fingerprinting, as well as for their compositional quantification. The range of materials investigated is very broad and encompasses painting materials, stones, glasses, ceramics, coatings on metals, paper and wooden materials, canvas or other textiles, organic colourants, resins, varnishes, cosmetics, and binding media such as glues, waxes, oils, etc . SR-IR-based methods can also be used to understand the historical technologies and to identify the raw materials used to produce archaeological artefacts and art objects, and to improve stabilization, conservation and restoration practices. Selected applications of SR-FTIR methods are discussed with a special emphasis on the chemical and mineralogical characterization of ancient paintings, on the study of alteration and corrosion layers, and the separation and identification of pigments. New perspectives offered by existing facilities and new developments in IR imaging and advanced vibrational spectroscopy that may broaden the variety of archaeological and historical materials that may be studied are outlined.