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Abstract *Sol-gel nanostructured titania materials have been reported to have applications in areas ranging from optics via solar energy to gas sensors. In order to enhance the photocatalytic activity, there are many studies regarding the doping of TiO 2 material with either nonmetals (S, C, N, P) or metals (Ag, Pt, Nd, Fe). The present work has studied some un-doped and Pd-doped sol-gel TiO 2 materials (films and gels), with various surface morphologies and structures, obtained by simultaneous gelation of both precursors Ti(OEt) 4 and Pd(acac) 2. Their structural evaluation and crystallization behaviour with thermal treatment were followed by DTA/TG analysis, IR spectroscopy, FTIR, spectroellipsometry (SE), XRD and AFM. The influence of Pd on TiO 2 crystallization both for supported and un-supported materials was studied (lattice parameters, crystallite sizes, internal microstrains). The changes in the optical properties of the TiO 2 -based vitreous materials were correlated with the changes of the structure. The hydrophilic properties of the films were also connected with their structure, composition, and surface morphology.