This paper reports on the aging of carbon nanowalls (CNW) and modification of their wettability by the storage time, growth conditions, and post‐fabrication plasma treatments. The as‐deposited CNW initially exhibit marked hydrophilic behavior (fresh CNW), but within a few days they become highly hydrophobic (aged CNW). Their final hydrophobicity is closely related to their topography which is controlled by the deposition parameters. In addition, subsequent fluorinated plasma treatments result in super‐hydrophobic CNW layers, irrespective of the hydrophilic or hydrophobic character of the pre‐treated samples. To explain this, we show that the CNW edges contain many defects initially, but such defects become passivated in time. As a result, the surfaces become highly hydrophobic after aging or fluorination, having inert stable terminations.