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The widespread use of distributed energy resources in the future electric distribution systems represents both a challenge and an opportunity for all the Smart Grid operators. Among these resources, plug-in electric vehicles are expected to play a significant role not only for the economic and environmental benefits they involve but also for the ancillary services they can provide to the supplying grid. This chapter deals with real-time operation of unbalanced microgrids including plug-in electric vehicles. The operation is achieved by means of an optimal control strategy aimed at minimizing the costs sustained for the energy provision while meeting various technical constraints. Among the technical constraints, the optimal control allows guaranteeing the satisfaction of power quality requirements such as the containment of slow voltage variations and the unbalance factors. Case studies are investigated in order to show the feasibility and the effectiveness of the proposed approach.