Nanosizing is a frequently applied strategy in recent years to improve storage properties of Li-ion electrodes and facilitate novel storage mechanisms. Due to particle size reduction, surface effects increasingly dominate, which can drastically change the storage properties. Using density functional theory calculations we investigate the impact of the surface environment on the Li-ion insertion properties in defective spinel Li(4+x)Ti(5)O(12), a highly promising negative electrode material. The calculations reveal that the storage properties strongly depend on the surface orientation. The lowest energy (1 1 0) surface is predicted to be energetically favorable for Li-ion insertion into the vacant 16c sites. The (1 1 1) surface allows capacities that significantly exceed the bulk capacity Li(7)Ti(5)O(12) at voltages greater than 0 V by occupation of 8a sites in addition to the fully occupied 16c sites. One of the key findings is that the surface environment extends nanometers into the storage material, leading to a distribution of voltages responsible for the curved voltage profile commonly observed in nanosized insertion electrode materials. Both the calculated surface-specific voltage profiles and the calculated particle size dependent voltage profiles are in good agreement with the experimental voltage profiles reported in literature. These results give a unique insight into the impact of nanostructuring and further possibilities of tailoring the Li-ion voltage profiles and capacities in lithium insertion materials.