Lithium-ion batteries on electric vehicles have been increasingly deployed for the enhancement of grid reliability and integration of renewable energy, while users are concerned about extra battery degradation caused by vehicle-to-grid (V2G) operations. This paper details a multi-year cycling study of commercial 24 Ah pouch batteries with Li(NiMnCo)O₂ (NCM) cathode, varying the average state of charge (SOC), depth of discharge (DOD), and charging rate by 33 groups of experiment matrix. Based on the reduced freedom voltage parameter reconstruction (RF-VPR), a more efficient non-intrusive diagnosis is combined with incremental capacity (IC) analysis to evaluate the aging mechanisms including loss of lithium-ion inventory and loss of active material on the cathode and anode. By analyzing the evolution of indicator parameters and the cumulative degradation function (CDF) of the battery capacity, a non-linear degradation model with calendar and cyclic aging is established to evaluate the battery aging cost under different unmanaged charging (V0G) and V2G scenarios. The result shows that, although the extra energy throughput would cause cyclic degradation, discharging from SOC 90 to 65% by V2G will surprisingly alleviate the battery decaying by 0.95% compared to the EV charged within 90–100% SOC, due to the improvement of calendar life. By optimal charging strategies, the connection to the smart grid can potentially extend the EV battery life beyond the scenarios without V2G.