During growth of multilayers by pulsed laser deposition (PLD), often both intermixing and resputtering occur due to the high kinetic energy of the particles transferred from the target to the substrate surface. In order to obtain a fundamental understanding of the underlying processes, W/Si multilayers have been studied by the complementary methods of transmission electron microscopy (TEM), X-ray reflectivity (XRR) and in-situ rate monitoring. For the experiments, deposition conditions were chosen that result in high energetic Si ions and mainly low energetic W atoms for the multilayer growth. Under these conditions, interface mixing of up to 3 nm occurs at the W/Si interfaces, while the Si/W interfaces remain sharp. Furthermore, enhanced resputtering of Si leads to a Si thickness deficit of up to 2 nm at the W/Si interfaces. The presented results can be understood by a combination of theoretical calculations as well as SRIM and TRIDYN simulations, which match perfectly to the experimentally obtained intermixing and enhanced resputtering of Si at the W/Si interfaces.