This paper proposes a novel hierarchical control architecture that combines Model Predictive Control (MPC) with Explicit Model-Following Control (EMFC) to enable accurate and efficient trajectory tracking for quadrotor electric Vertical Takeoff and Landing (eVTOL) aircraft operating in urban environments. The approach addresses the challenges of strong nonlinear dynamics, multi-axis coupling, and stringent safety constraints by separating the planning task from the fast-response control task. The MPC layer generates constrained velocity and yaw rate commands based on a simplified inertial prediction model, effectively reducing computational complexity while accounting for physical and operational limits. The EMFC layer then compensates for dynamic couplings and ensures the rapid execution of commands. A high-fidelity simulation model, incorporating rotor flapping dynamics, differential collective pitch control, and enhanced aerodynamic interference effects, is developed to validate the controller. Four representative ADS-33E-PRF tasks—Hover, Hovering Turn, Pirouette, and Vertical Maneuver—are simulated. Results demonstrate that the proposed controller achieves accurate trajectory tracking, stable flight performance, and full compliance with ADS-33E-PRF criteria, highlighting its potential for autonomous urban air mobility applications.