In Portland cement mortars it is of paramount importance to investigate the bond strength between mortar and masonry by means of the study of interfaces and surfaces that make up the system mortar/ceramic block. In this work the aim was to characterize the chemical compositions, microstructures, surfaces and interfaces of mortars applied on ceramic blocks. Therefore, two important characterization tools were used: field-effect gun (FEG) scanning electron microscope (SEM) - FEI Quanta 200 with energy-dispersive (X-ray) spectrometer (EDS) and SEM system with EGF Nanofabrication FIB - FEI Quanta 3D FEG also with an EDS coupled. To date the results obtained from the research show that the characterization of cementitious materials with high resolution SEM is an important tool in the detection and differentiation of hydrated calcium silicates (CSH), calcium hydroxide (Ca(OH)2), ettringite and calcium carbonate by means of morphological, topographical and chemical data, thus providing extremely reliable as well as qualitative data from the structure of cementitious materials.