A new heteroleptic titanium precursor with a mixed oxygen/nitrogen coordination sphere [Ti(dmap)₂(NMe₂)₂] (Hdmap=1-dimethylamino-2-propanol) is synthesized by a simple elimination reaction on tetrakis-dimethylaminotitanium(IV) [Ti(NMe₂)₄]. The compound shows encouraging results in terms of chemical and thermal stability compared to the parent alkyl amide [Ti(NMe₂)₄], and is therefore more suitable for MOCVD applications. TiO₂ thin films are grown on Si(100) and ITO-coated borosilicate glass substrates via MOCVD in the temperature range 500-800°C. The deposition temperature has a significant effect on the phase and microstructure of the TiO₂ films obtained, which influences the functional properties. The optical bandgaps of the films are in the range 2.92-3.36eV. The best photocurrent response (1.5mAcm^-2 under AM 1.5G conditions) in aqueous electrolytes is observed for films grown at 700°C having improved crystallinity and porous columnar structure.