PV hosting capacity of a practical three-phase unbalanced distribution network is expected to increase, thus increasing safe PV penetration and speeding up the decarbonization of power systems. However, power unbalances and bus voltage violations are two major obstacles limiting further increases in the PV hosting capacity. With the popularization of electric vehicles (EVs), EV charging stations (EVCSs) as controllable loads can effectively provide grid ancillary services, which helps enhance the PV hosting capacity. In this regard, this paper proposes a hierarchical control method for EVCSs in an unbalanced network, consisting of central day-ahead scheduling and local real-time dynamic control. It is novel that the local control capability of EVCSs is reserved in the central scheduling. A three-phase day-ahead EV charging scheduling optimization model is developed to reduce the power unbalance and the bus voltage violation, and in turn, improve the PV hosting capacity. Moreover, active power transfer and voltage droop control are developed as two ancillary service functions for local real-time control responding to dynamic network operating conditions. Numerical simulations verify the effectiveness of the proposed method in enhancing PV hosting capacity and providing grid ancillary services.