Tailsitter unmanned aerial vehicles are utilized extensively nowadays since they merge advantages of both fixed-wing unmanned aerial vehicles and rotary-wing unmanned aerial vehicles. However, their attitude control suffers from unknown nonlinearities and disturbances due to the wide flight envelope. To solve the problems, a robust attitude controller based on a newly designed flying-wing tailsitter is proposed in this paper. By employing the angular acceleration feedback to compensate unmodeled dynamics, the proportional incremental nonlinear dynamic inversion control law is first developed. The proportional incremental nonlinear dynamic inversion strengthens the conventional nominal gain incremental nonlinear dynamic inversion with a proportional term to reflect the change of the angular acceleration more directly. Therefore, the tailsitter has a quicker response and performs better in suppressing model uncertainties and external disturbances. Since the angular acceleration is difficult to measure in practice, an angular acceleration estimation method is then established to provide accurate signals for the proportional incremental nonlinear dynamic inversion. The signals are derived as complementary results of model prediction method and direct differential method. Theoretical analysis and systematic simulations are conducted to corroborate the effectiveness of the developed estimation method as well as the robustness of the proposed controller.