An important factor that governs solar energy transformation into electrical or chemical energy, when using nanoparticles-based devices, is the spatial location of traps limiting electron transport. Evidences have been presented indicating that the electron diffusion is strongly influenced by nanoparticle boundaries, whose characteristics depend on the particles preparation. In the present work we have studied the role of hydrated excess proton structures in the formation of anatase nanoparticles boundaries in samples prepared by TiCl4 hydrolysis at low temperature and strong acidic conditions. The samples, constituted by anatase nanocrystals but, mainly, by amorphous titania, are studied by H-1-MAS NMR, FT-IR and HRTEM. The results indicate that hydrated excess proton species, generated by solvation of bridging hydroxyls protons of highly defective anatase and/or amorphous titania chains, favor the chains bonding to anatase nanoparticles and/or their condensation at the nanoparticles surface. The chains' bonding facilitates the anatase particles aggregation producing oriented self-assemblings. The preparation conditions determine a strong condensation of amorphous titania chains and it should favor anatase transformation into rutile. (C) 2016 Elsevier B.V. All rights reserved.