Four major toners are used in the printing industry, cyan, magenta, yellow and black (Key) for making color images on paper. Paper brands suitable for printing have thin mineral/latex coatings, and toners are applied on top of the coating in the printing process. Chemical compositions from toner to toner, as well as from coating to coating, vary according to the needs of the end user. Interactions between the toner and the coating define the final color formation of the images in printing. Hence, it is important to study characteristics and dynamics of toners on coated papers. In this paper, we have used laser-induced plasma spectroscopy (LIBS) to provide information on elemental distributions of the toner and the coating layers on three coated papers and the base paper at a sub-micrometer resolution. Ablation crater depth profiles in the three different material layers were converted into metric scale by combining elemental information from the LIBS measurements and optical profilometry. Ablation efficiencies for a toner of 150 nm/pulse, for a coating of approximately 350 nm/pulse and for a base paper of approximately 1 μm at a fluence of 0.6 J/cm2 of an ArF excimer laser were determined. Using these results, the average layer thicknesses of the toner and the coating layers were evaluated. The detailed analysis of the elemental profiles of the two cyan toners studied revealed strong accumulation of silicon and titanium compounds of the toner on the toner–air interface but also on the toner–coating interface, but to a much smaller extent. The observation reveals the significance of toner component diffusion due to substrate–machine interaction in the printing process. Such diffusion processes must have an important role in final color formation of the images in printing. The method developed provides a unique and accurate means to study toner diffusion processes in coated papers under printing conditions.