A new approach for the detection and visualization of nano-scaled film defects, such as fissures and holes is described. The procedure is based on a selective electrochemical deposition of bismuth onto uncovered parts of stainless steel substrates due to film cracking after deformation. Cyclic voltammetry experiments enabled the identification of the bismuth redox signals, necessary for the subsequent potentiostatic electrodeposition. A combination of XPS and ToF-SIMS analyses demonstrated that deposition with commonly used acidified electrolytes led to a significant film degradation, by defluorination and chain scission. When an identical procedure was performed in neutral conditions, which was realized by the addition of a bismuth chelating agent, no influence onto the integrity of the fluorocarbon coatings was observed. By SEM, XPS and ToF-SIMS analyses, the deposition of bismuth on the film defects was clearly demonstrated and the failures were evidenced. The identification of nano-scaled coating failures, which was extremely difficult before using common characterization tools, was now realized. This work makes part of a strategy to cover stent materials with a protective fluorocarbon layer and to examine the influence of stent expansion onto the film cohesive properties. (C) 2009 Elsevier Ltd. All rights reserved.