The detailed surface chemistry of aluminum oxide protected silver films for use specifically in surface enhanced Raman spectroscopy and tip enhanced Raman spectroscopy (TERS) was investigated. We have demonstrated that increased storage and scanning use lifetimes for silver plasmonic structures are directly connected with the elimination of chemical degradation at the plasmonic structure surface. X-ray photoelectron spectroscopy of the metal films confirmed that a 2–3 nm thick coating of aluminum oxide prevented chemical attack of the underlying silver film for three months of storage in a desiccator, significantly increasing the storage lifetime of current probes. The scanning lifetime of a TERS probe when used to image a hard patterned silicon substrate was doubled with the addition of this protective coating. These measurements were performed without laser illumination in order to separate laser-induced heating degradation from pure mechanical degradation of the metallized probe currently encountered during TERS data collection. Copyright © 2013 John Wiley & Sons, Ltd.