For the first time, the sol-gel method was coupled with electrostatic spray deposition (ESD) to fabricate nanotextured bioactive glass (BG) coatings with a controlled microstructure in a one-pot-process. Three BG compositions belonging to the SiO2-CaO-P2O5 system (S85, S75, and S58) were homogeneously deposited on metallic Ti6Al4V substrates starting from the atomization of precursor solutions. All coatings displayed an amorphous character, as confirmed by XRD. A wide variety of innovative BG morphologies were obtained, tuning the key parameters of ESD, leading from highly porous coral-like to compact reticular-type coatings. The bioactivity, in terms of apatite formation, of as-deposited coatings was tested by immersion in simulated body fluid solution. Textural properties were found to play an important impact in its biological performance. Highly porous ESD-coatings exhibited remarkable bioactivity for S75 and S58 compositions, compared with more compacted ones of equal formulations. S85 composition was found extremely reactive regardless of the coating microstructure.