Angle-scanned X-ray photoelectron diffraction (XPD) and scanning tunneling microscopy (STM) are used to characterise the structure of TiO2 nanoparticles grown on a Pt(111) single crystal surface. The nanoparticles grow over a well-ordered oxide interfacial layer that displays a (square root 43 x square root 43) - R7.6 degrees superstructure with a unit cell (18.2 x 18.2 A), as demonstrated by STM and low-energy electron diffraction (LEED). Our XPS Ti 2p core level spectra suggest a significant contribution from reduced titanium ions within the interfacial layer. On the contrary, according to XPS binding energy data, the nanoparticles are mostly composed of Ti(IV) ions. During the initial stage of the growth, the nanoparticles are on the average 2 nm high and about some tens of nm wide, and show a flat on-top surface, while the interparticle region show the structure of the ordered interfacial layer. During later stages of the deposition, the particles become larger and they show a more irregular, globular-like shape as well as coalescence. But, even at this stage of the growth, large interparticle regions are present. Moreover, the nanoparticles produce a distinct XPD pattern which demonstrates that they grow with a preferential azimuthal orientation with respect to the substrate surface. A simple geometrical analysis of the XPD data in terms of forward scattering events suggests that the particles crystallize in the rutile TiO2 structure and expose the (100) surface. This hypothesis is supported by means of multiple scattering simulations of the XPD patterns.