A mathematical model for all-solid-state Li-ion batteries is presented. The model includes the charge transfer kinetics at the electrode/electrolyte interface, diffusion of lithium in the intercalation electrode, and diffusion and migration of ions in the electrolyte. The model has been applied to the experimental data taken from a 10 mu Ah planar thin-film all-solid-state Li-ion battery, produced by radio frequency magnetron sputtering. This battery consists of a 320 nm thick polycrystalline LiCoO2 cathode and a metallic Li anode separated by 1.5 mu m Li3PO4 solid-state electrolyte. Such thin-film batteries are nowadays often employed as power sources for various types of autonomous devices, including wireless sensor nodes and medical implants. Mathematical modeling is an important tool to describe the performance of these batteries in these applications. The model predictions agree well with the galvanostatically measured voltage profiles. The simulations show that the transport limitations in the solid-state electrolyte are considerable and amounts to at least half of the total overpotential. This contribution becomes even larger when the current density reaches 0.5 mA cm(-2) or higher. It is concluded from the simulations that significant concentration gradients develop in both the positive electrode and the solid-state electrolyte during a high current (dis)charge. (C) 2010 The Electrochemical Society. [DOI:10.1149/1.3521414] All rights reserved.