In recent years, great attention has been paid on Electric Vehicles (EVs) in terms of environmental pollution. Here, EVs can greatly reduce the environmental pollution, compared with traditional Internal Combustion Vehicles (ICVs). However, since EVs cannot be replenished fast like ICVs, the rigid deployment of charging infrastructure and its limited charging capability, leads to service congestion particularly due to a large number of EVs being parked with charging demand. Compared to CSs with rigid extension in location and charging facilitates, the Vehicle-to-Vehicle (V2V) charging service provides a spatial and temporal advance in flexibility, with potential to supplement with G2V charging mode, which can supplement or even replace the G2V Charging Mode. In this paper, we propose a hybrid V2V charging scheme, consisting of direct and asynchronous V2V charging modes, to achieve a great charging flexibility and alleviate the burden for grid load. Here, we estimate the Minimum Waiting Time (MWT) under each mode, as guidance to switch between modes and optimize charging service under each mode. Results show that our proposed hybrid V2V charging scheme outperforms literature works, in terms of average waiting time and number of full charged EVs.