Nanophase TiO2 has been synthesized in an organic medium by two different routes, yielding two different structural phases viz. rutile and anatase. These differences are reflected in the different characterization techniques used to study the nanoparticles. UV-vis spectroscopy shows absorption-peak related particle sizes of similar to 2.5 nm and agrees with transmission electron microscopy (TEM) estimates of 2.5-5.0 nm. Grazing incidence X-ray diffraction shows rutile and anatase phase with an overlay of Ti2O3 for the different routes considered. Differences in the nature of the transition from absorption plots not withstanding, a direct transition is confirmed. Photo-luminescence (PL) spectra for the two particulate structures shows prominent red shifted peaks at 314 nm and 399 nm, respectively (0.81 eV from the excitation), and also reveals vibrational features around the maximum PL signal. In addition a Ti3+ (PL) state is observed at 617.5 nn for both cases, a feature governed by the Auger process. Fourier transform infrared (FTIR) studies reveal weak complex vibrations between the Ti-O oxide species and also additional unsaturated sites (Ti3+) through incorporation of (OH) groups, not otherwise seen in bulk titania. A surface consisting of Ti-6(3+)-OH for coordinative saturation (octahedral site), along with Ti-4(4+)-O (tetrahedral) is thus necessary. Grazing incidence X-ray diffraction studies shows the presence of the rutile phase of TiO2 and also a sub-oxide phase of Ti (Ti2O3) X-ray photoemission spectre (XPS) of thin films of TiO2 confirms the oxide phase and also the presence of sub-valence states. The XPS and FTIR. spectra confirm the presence of adsorbed sites for coordinative saturation of sub-valence states (Ti2+, Ti3+), through hydroxyl incorporation. These sites are amplified as the particle size is reduced, opening avenues for additional coordination, leading to important applications. In this case, a Ti2O3 overlay saturates the surface of titania. Subtle differences are observed in the data vis-a-vis literature reports.