  The wealth of properties of titanium dioxide relies on its various polymorphs
and on their mixtures coupled with a sensitivity to crystallographic
orientations. It is therefore pivotal to set out methods that allow surface
structural identification. We demonstrate herein the ability of photoemission
spectroscopy to provide Ti LMV (V = valence) Auger templates to quantitatively
analyze TiO$_2$ polymorphs. The Ti LMV decay reflects Ti 4sp-O 2p
hybridizations that are intrinsic properties of TiO$_2$ phases and
orientations. Ti LMV templates collected on rutile (110), anatase (101), and
(100) single crystals allow for the quantitative analysis of mixed nanosized
powders, which bridges the gap between surfaces of reference and complex
materials. As a test bed, the anatase/rutile P25 is studied both as received
and during the anatase-to-rutile transformation upon annealing. The agreement
with X-ray diffraction measurements proves the reliability of the Auger
analysis and highlights its ability to detect surface orientations.
