Inappropriate posture and the presence of spinal disorders require specific monitoring systems. In clinical settings, posture evaluation is commonly performed with visual observation, electrogoniometers or motion capture systems (MoCaps). Developing a measurement system that can be easily used also in non-structured environments would be highly beneficial for accurate posture monitoring. This work proposes a system based on three magneto-inertial measurement units (MIMU), placed on the backs of seventeen volunteers on the T3, T12 and S1 vertebrae. The reference system used for validation is a stereophotogrammetric motion capture system. The volunteers performed forward bending and sit-to-stand tests. The measured variables for identifying the posture were the kyphosis and the lordosis angles, as well as the range of movement (ROM) of the body segments. The comparison between MIMU and MoCap provided a maximum RMSE of 5.6° for the kyphosis and the lordosis angles. The average lumbo-pelvic contribution during forward bending (41.8 ± 8.6%) and the average lumbar ROM during sit-to-stand (31.8 ± 9.8° for sitting down, 29.6 ± 7.6° for standing up) obtained with the MIMU system agree with the literature. In conclusion, the MIMU system, which is wearable, inexpensive and easy to set up in non-structured environments, has been demonstrated to be effective in posture evaluation.