To achieve a broader public acceptance for electric vehicles based on lithium-ion battery (LIB) technology, long driving ranges, low cost, and high safety are needed. A promising pathway to address these key parameters lies in the further improvement of Ni-rich cathode materials for LIB cells. Despite the higher achieved capacities and thus energy densities, there are major drawbacks in terms of capacity retention and thermal stability (of the charged cathode) which are crucial for customer acceptance and can be mitigated by protecting cathode particles. We studied the impact of surface modifications on cycle life and thermal stability of LiNi0.90Co0.05Mn0.05O2 layered oxide cathodes with WO3 by a simple sol–gel coating process. Several advanced analytical techniques such as low-energy ion scattering, differential scanning calorimetry, and high-temperature synchrotron X-ray powder diffraction of delithiated cathode materials, as well as charge/discharge cycling give significant insights into the impact of surface coverage of the coatings on mitigating degradation mechanisms. The results show that successful surface modifications of WO3 with a surface coverage of only 20% can prolong the cycle life of an LIB cell and play a crucial role in improving the thermal stability and, hence, the safety of LIBs.