Off-stoichiometric copper chromium delafossites demonstrate the highest values of electric conductivity among the p-type transparent conducting oxides. Morphological and structural changes in cu 0.66 cr 1.33 o 2 upon annealing processes are investigated. chained copper vacancies were previously suggested as source of the high levels of doping in this material. High resolution Helium ion Microscopy, Secondary ion Mass Spectrometry and transmission electron Microscopy reveal a significant rearrangement of copper and chromium after the thermal treatments. Furthermore, positron Annihilation Spectroscopy evidences the presence of vacancy defects within the delafossite layers which can be assigned to the cu vacancy chains whose concentration decreases during the thermal process. These findings further confirm these chained vacancies as source of the p-type doping and suggest that the changes in electrical conductivities within the off-stoichiometric copper based delafossites are triggered by elemental rearrangements. P-type transparent conductive oxides (TCOs) have lately attracted attention due to their promising applications in various fields such as flat panel displays, solar cells, photovoltaics and transparent electronic devices. The development of such material, with properties similar to its n-type counterpart (electric conductivity 10 3 S cm −1 , optical transmittance in the visible range well above 80%) will unlock the fabrication of a complete transparent active device (like a diode or a transistor) 1,2. Among the others TCOs, copper based delafossites (with general formula CuM 3+ O 2 , where M = Al, Cr, B, Ga or In) have shown attractive performances with a record value of electric conductivity of 280 S cm −1 (with a visible transmittance of 50%) 3,4. In such delafossites, the mixing of Cu 3d states and O 2p states forming the valence band leads to higher holes mobility. Tailoring the edge of the valence band by mixing molecular orbitals of the cations was proposed by Hosono and co-workers and demonstrated for CuAlO 2 as the first p-type transparent delafossite 5,6. Among delafossite materials, a special focus was given to CuCrO 2 due to its highest density of 3d cations near the maximum of valence band and the covalent mixing between chromium and oxygen ions 7. These two properties shall promote larger holes mobility and hence greater conductivities are expected for this material. However, intrinsic CuCrO 2 presents a relatively low conductivity (10 −4 S cm −1) and doping is required for obtaining decent electrical conductivity larger than 1 S cm −1 8. Higher values started to be lately reported for delafossite films demonstrating peculiar off-stoichiometric ratios. Tens of