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This paper presents a viable quaternion-based complementary observer (CO) that is designed for rigid body attitude estimation. We claim that this approach is an alternative one to overcome the limitations of the extended Kalman filter. The CO processes data from a small inertial/magnetic sensor module containing triaxial angular rate sensors, accelerometers, and magnetometers, without resorting to GPS data. The proposed algorithm incorporates a motion kinematic model and adopts a two-layer filter architecture. In the latter, the Levenberg Marquardt algorithm preprocesses acceleration and local magnetic field measurements, to produce what will be called the system's output. The system's output together with the angular rate measurements will become measurement signals for the CO. In this way, the overall CO design is greatly simplified. The efficiency of the CO is experimentally investigated through an industrial robot and a commercial IMU during human segment motion exercises. These results are promising for human motion applications, in particular future ambulatory monitoring.