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This paper presents a new technique of electrical energy generation using mechanically excited piezoelectric materials and a nonlinear process. This technique, called synchronized switch harvesting (SSH), is derived from the synchronized switch damping (SSD), which is a nonlinear technique previously developed to address the problem of vibration damping on mechanical structures. This technique results in a significant increase of the electromechanical conversion capability of piezoelectric materials. Comparatively with standard technique, the electrical harvested power may be increased above 900%. The performance of the nonlinear processing is demonstrated on structures excited at their resonance frequency as well as out of resonance.