Experimental studies of concentration profiles in W/C and Ni/C multilayers prepared by pulsed laser deposition are compared with ballistic simulations of the deposition process by means of the computer code TRIDYN. One part of the deposited particles possesses kinetic energies of about 100 eV and leads to a ballistic mixing of the deposited layers. As a consequence, diffuse interface concentration profiles arise and the concentrations within the individual layers depend on the layer thickness. The concentration profiles can be highly asymmetric between adjacent interfaces as observed e.g. in W/C multilayers. Simulations predict that the interface width for the deposition of W onto C is up to 3.5 times larger than in the opposite case. Differences between simulation results and HREM, AES, X‐ray and XPS studies suggest that the resulting interface concentration profiles are essentially influenced by compound formation as well as by demixing of components occurring during deposition.