The objective of this paper is to present systematic methods for throwing motion control of underactuated robots. The Pendubot, an underactuated two-link planar robot, is investigated as a dynamic model of the superior limbs for imitation of human throwing motion whose models are fundamentally underactuated in nature. The controller is designed based on input-output linearization and output zeroing control. The originality of this paper is to intentionally destabilize the zero dynamics, a nonlinear dynamics which remains unobservable from the designed output, to generate dynamic acceleration of the ball. Numerical simulations validate the effectiveness of the proposed control strategy.