The properties of oxide formed on pure aluminium in acetate buffers under controlled potential, temperature, and pH are characterized by in situ electrochemical techniques and spectroscopic visual ellipsometry (VISSE). Monitoring the current density (cd) during transition between different applied potentials gives direct information about Faradaic changes in the oxide properties, while the ellipsometer monitors the changes in the actual thickness and refractive index of the film. Electrochemical impedance spectroscopy (EIS) reveals, in addition to film properties, information about the charge transfer processes and adsorption at steady-state conditions. VISSE and ex situ transmission electron microscopy (TEM) indicate the presence of a two layered oxide structure, consisting of the barrier and a porous hydrated layer. The thickness and density of these two layers are monitored in situ during growth and dissolution. The thickness of the barrier layer depends reversibly on the applied potential, while the thickness of the hydrated layer is less affected by the potential. The absorption sensitive parameter is correlated with the buffer concentration and therefore believed to be related to the acetate.