Both conservation and intervention methods must be compatible with each other and appropriate for the original building materials. Therefore, the characterization of historic building materials is indispensable for investigating chemical composition, micro-structure and morphological features to study the current condition, environmental influence and change mechanism due to natural aging or man-made decay processes. Given the great variety of chemicals which can be analyzed, complex problems related to architectural heritage materials are investigated via optimized methodologies. Among the existing techniques, optical microscopy (OM) is an inexpensive and dominating tool to obtain preliminary information on complex samples. Atomic force microscopy (AFM) can provide real three-dimensional topographies showing sample surface properties. Electron microscopes combined with energy dispersion X-ray analysis (EM-EDX) are the instruments specifically developed to acquire images of target materials at high magnification. Infrared and Raman spectroscopies are frequently used to characterize inorganic and organic compounds. Thermal analysis can rapidly and accurately measure changes in crystalline structure, dehydration and decomposition. X-ray based technologies have a wide range of applications as follows. X-ray fluorescence (XRF) is one of the most frequently used techniques for elemental analysis. X-ray diffraction (XRD) is a fast and inexpensive technique for the characterization of man-made and natural materials. X-ray photoelectron spectroscopy (XPS) is applied to quantify the valence and electronic levels of specific elements. X-ray absorption spectroscopy (XAS) is a powerful technique for detecting the electronic structure of matter. UV-visible (UV-vis) spectroscopy is also of great importance in architectural heritage, which can reveal different physicochemical mechanisms causing color. Laserinduced breakdown spectroscopy (LIBS) can effectively eliminate the pollution on the surface and detect the internal elements of the target material. Ion beam analysis can quantify trace elements with high sensitivity. Mass-based techniques are mainly applied to identify unknown organic substances at the molecular level. This review describes some classical applications of individual techniques and provides scientific support for scientists and engineers to make decisions in the context of architectural heritage.