The investigation and analysis of polymer thin films with Bi(n)(+), n = 1-7 cluster ions has been demonstrated by means of static secondary ion mass spectrometry (SIMS). The highly specific signal enhancement of these primary ions combined with the individual fragmentation pattern of poly(4-vinylphenol) and poly(methyl methacrylate) is the basic principle for a modified approach of data reduction derived from the well-established g-SIMS procedure. Based on mass spectra, which correspond to different cluster ion sizes, not only a clear distinction between the two polymers is feasible but also a further simplification of the data can be demonstrated. It has been successfully proven that characteristic polymer-relevant species can be refined out of the large amount of unspecific and highly fragmented secondary ions, which are usually present in SIMS spectra. Therefore, a more precise and direct interpretation of complex organic fragments becomes feasible, which consequently enables the investigation of even more sophisticated samples.