The structure and photocatalytic activity of Zr doped TiO2 nanocrystallites with a varying Zr content between 0 and 15 wt% prepared by an efficient and environmentally benign method has been Studied by vibrational spectroscopy, TEM and XRD. It is shown that the presence of Zr4+ ions stabilizes the anatase structure and delays phase transformation to rutile upon annealing as well as retarding grain coarsening. All TiO2 samples up to 13 wt% Zr doping concentration show better or similar photoreactivity compared to P25 (Degussa) for decomposition of adsorbed 2-chloroethyl ethyl sulphide (CEES) and dimethyl methylphosphonate (DMMP) in synthetic air at room temperature. The most efficient sample for photodegradation of both CEES and DMMP is shown to be titania doped with 6.8 wt% Zr. The photodegradation of CEES is faster than DMMP under the same experimental conditions. On the undoped TiO2 sample urea residues are detected spectroscopically. Much less is detected on the Zr doped samples. Mode resolved in situ FTIR surface spectroscopy enables distinction of CEES or DMMP, decomposition products as well as the influence of residues from the particle synthesis. This facilitates extraction of intra-comparable reaction rates. Possible explanations for the improved reactivity of the Zr doped titania are discussed. (C) 2009 Elsevier B.V. All rights reserved.