Accurate determination of the performance and precise prediction of the state of health (SOH) of lithium-ion batteries are necessary to ensure reliability and efficiency in real-world application. However, most SOH offline studies were based on dynamic stress tests, which only reflect the universal rule of degradation, but are not necessarily applicable for real-world applications. This paper presents an experimental evaluation of two different operations of real-world plug-in hybrid electric vehicles with LiFePO₄ batteries as energy-storage systems. First, the LiFePO₄ batteries were subjected to a set of comparative experimental tests that consider the effects of charge depleting (CD) and charge sustaining (CS) operations. Then, different voltage analysis along with the close-to-equilibrium open circle voltage was utilized to evaluate the performance of the batteries in life cycles. Finally, a qualitative relationship between the external factors (the percentage of time of CD/CS operations during the entire driving range) and the degradation mechanism was built with the help of the proposed methods. Results indicated that the external factors affect the degree of the batteries degradation, but not up to the point when the capacity fading stage occurs. This relationship contributes to the foundation for plug-in hybrid electric vehicles’ (PHEVs’) energy management strategy or battery management system control strategy.