The growing interest in Electrical Vehicles (EVs) opens new possibilities in the use of Li-ion batteries in order to provide ancillary grid services while they are plugged to recharging stations. Indeed, Vehicle-to-Grid (V2G), Vehicle-to-Building (V2B), Vehicle-to-Home (V2H) as well as Vehicle-to-Vehicle (V2V) services can be carried out depending on the particular installation and on the connection to the distribution grid of the considered recharging station. Even if these are interesting and challenging opportunities, the additional charging/discharging cycles necessary to provide these services could decrease the expected life of EV batteries. For this reason, it is of paramount importance to study and develop reliable models of the batteries, which take the aging phenomena affecting the reliability of the Li-ion cells into account to evaluate the best charging/discharging strategy and the economic revenues. To this aim, this paper focuses on a battery pack made up with Li-ion nickel–manganese–cobalt (NMC) cells and proposes a semiempirical Electrothermal Aging Model, which accounts for both calendar and cycle aging. This modeling phase is supported by several experimental data recorded for many charge and discharge cycles at different C-rates and for several temperatures. Thus, it is possible to analyze and compare scenarios considering V2G services or not. Results show that the considered battery is subjected to a life reduction of about 2 years, which is a consequence of the increased Ah charge throughput, which moves from 120,000 Ah over 10 years (scenario without V2G services) to almost 230,000 Ah over 8 years (scenario with V2G services).