Aluminosilicate materials were obtained by sol-gel method, using different Al2O3 and SiO2 precursors in order to prepare sols based on water and organic solvents. As SiO2 precursors, Aerosil 200TM and tetraethoxysilane TEOS: Si(OC2H5)4 were applied, while DisperalTM and aluminium secondary butoxide ATSB: Al(OC4H9)3 were used for Al2O3 ones. Bulk samples were obtained by heating gels at 500 °C, 850 °C and at 1150 °C in air, while thin films were synthesized on carbon, steel and alundum (representing porous ceramics) substrates by the dip coating method. Thin films were annealed in air (steel and alundum) and in argon (carbon) at different temperatures, depending on the substrate type. The samples were synthesized as gels and coatings of the composition corresponding the that of 3Al2O3·2SiO2 mullite because of the specific valuable properties of this material. The structure of the annealed bulk samples and coatings was studied by FT-IR spectroscopy and XRD method (in standard and GID configurations). Additionally, the electron microscopy (SEM) together with EDS microanalysis were applied to describe the morphology and the chemical composition of thin films. The analysis of FT-IR spectra and X-ray diffraction patterns of bulk samples revealed the presence of γ-Al2O3 and δ-Al2O3 phases, together with the small amount of SiO2 in the particulate samples. This observation was confirmed by the bands due to vibrations of Al–O bonds occurring in γ-Al2O3 and δ-Al2O3 structures, in the range of 400 to 900 cm−1. The same phases (γ-Al2O3 and δ-Al2O) were observed in the deposited coatings, but the presence of particulate ones strongly depended on the type of Al2O3 and SiO2 precursor and on the heat treatment temperature. All thin films contained considerable amounts of amorphous phase.