A simple and effective way for TiO(2) to be deposited on silicon or indium tin oxide (ITO) substrates has been achieved by using a poly(styrene-block-4-vinyl pyridine) (PS-b-P4VP) block copolymer template. In particular, a mechanism for the formation of TiO(2) within the P4VP phase was developed. Within this model, the TiO(2) deposition occurs by swelling of the protonated P4VP segments followed by transport of Ti precursor, probably protonated Ti(OH)(4) given the low pH conditions used, into the swollen P4VP followed by condensation into TiO(2) during the heating/plasma etch processes. TiO(2) nanostructure morphology is affected by pH and deposition temperatures, because these parameters affect the degree of protonation of P4VP segments and diffusion of the titanium(IV) bis (ammonium lactato)dihydroxide (TALH) precursor into the film. A pH range of 2.1-2.5 for silicon substrates and pH = 2.1 for ITO substrates gave the narrower TiO(2) nanostructures distributions, and deposition at 70 degrees C gave TiO(2) nanostructures with more regular arrangements and smoother surface than those deposited at room temperature. The use of 1,4-diiodobutane as a P4VP cross-linking compound is demonstrated to be a critical parameter for maintaining good cylindrical surface morphology for both the block copolymer template and the TiO(2) nanostructures.