Abstract This paper describes the applicability and limitations of time‐of‐flight secondary ion mass spectroscopy (ToF‐SIMS) for the analysis of paper samples based on studies related to fine papers used in the cigarette industry. The focus was on imaging and appropriate ways of image processing and image analysis. Paper cross‐sections were prepared in different ways to analyse the distribution of individual fillers in a paper sheet and to characterise the distribution of the adhesive between paper layers after further processing. As filler distribution in the z ‐direction influences important paper properties like opacity or printability, the first part of the study should help paper manufacturers to optimise pigment distribution for a proper control of the desired paper characteristics. In the second part, the impact of various parameters (paper sizing, glue viscosity, machine settings) on the distribution of adhesives between paper layers in the finished product is investigated after further processing by cigarette makers. Statistical analysis of the data reveals some of the complex interactions of these parameters and confirms and quantifies many facts known only from experience in paper making, paper processing and cigarette manufacture. Copyright © 2006 John Wiley & Sons, Ltd.