In the aspect of further development of investigations in the area of spacecraft modeling and analysis of the control scheme, a new hybrid finite-time robust three-axis cascade attitude control approach is proposed via pulse modulation synthesis. The full quaternion based control approach proposed here is organized in association with both the inner and the outer closed loops. It is shown that the inner closed loop, which consists of the sliding mode finite-time control approach, the pulse width pulse frequency modulator, the control allocation and finally the dynamics of the spacecraft is realized to track the three-axis referenced commands of the angular velocities. The pulse width pulse frequency modulators are in fact employed in the inner closed loop to accommodate the control signals to a number of on–off thrusters, while the control allocation algorithm provides the commanded firing times for the reaction control thrusters in the overactuated spacecraft. Hereinafter, the outer closed loop, which consists of the proportional linear control approach and the kinematics of the spacecraft is correspondingly designed to deal with the attitude angles that are presented by quaternion vector. It should be noted that the main motivation of the present research is to realize a hybrid control method by using linear and nonlinear terms and to provide a reliable and robust control structure, which is able to track time varying three-axis referenced commands. Subsequently, a stability analysis is presented to verify the performance of the overall proposed cascade attitude control approach. To prove the effectiveness of the presented approach, a thorough investigation is presented compared to a number of recent corresponding benchmarks.