This paper describes a method using attenuated total reflectance infra-red spectroscopy to determine the surface concentration of calcium carbonate in paper samples, by applying the linear relationship between the relative infra-red absorption integrals and the concentration. The method was able to detect micro-variations in the surface concentration and could also distinguish between different sheets as well as between the top and bottom side of one sheet. The samples were also split and the calcium carbonate concentration was determined within and compared to bulk calcium carbonate concentration determined from ash testing. The surface results were also compared with analysed scanning electron microscopy images generated from back-scattering electrons. The comparison shows that both sets of results are in excellent agreement. Depending on the sample, large errors (95 confidence) were observed. These, however, are caused by micro-variations of the surface concentration, rather than by inaccuracies of the technique, which is estimated to be less than 1 . Furthermore, measurements of various sample orientations suggest that anisotropic polarisation effects can be neglected. The method can be applied to paper and cellulose matrices having calcium carbonate filler contents of less than 50 . Due to spectral overlaps it is not suitable to determine kaolin filler contents.