This work deals with the determination of the semiconducting properties of a galvanostatically anodised Ti electrode. being in contact with solutions containing silver complexing agents. The Ti/TiO2/electrolyte interfaces are-in a first attempt-characterised in contact with silver-free baths. so that during cathodic polarisation no silver electrodeposition occurs and the system can be studied under (quasi-) stationary conditions. On the basis of a. ell-considered data analysis of potential-dependent Impedance Measurements, it is possible to estimate the interfacial characteristics (apparent flatband potential. V-fb, and density of multiple donor levels in the space charge region. N-SC). On its turn. it allows to characterise the modes' the highly defective oxide film is brought into, both as a function of the applied potential and the used type of ligand.