The present work presents the investigation of the dynamics and influence of chaotic behavior on energy capture for a U-shaped structure (portal frame) that contains shape memory alloy (SMA), piezoelectric material (PZT), a nonlinear energy sink (NES) and a non-ideal excitation source represented by an unbalanced electric motor coupled to the U-structure. The mathematical model presents nonlinearities arising from the nonlinear stiffness of the U-structure, the NES system, the SMA, and the PZT material. Chaotic behavior is assessed through time history, bifurcation diagrams, phase diagrams, and the 0–1 test. Energy capture is carried out through a piezoelectric material (PZT), represented by a non-linear electromechanical coupling model, and electromagnetic induction generated by the non-linear electromagnetic energy sink coupled to the structure (NES). Dynamic analysis is performed through parametric analysis of parameters related to piezoelectric coupling and NES parameters. Numerical simulations demonstrate that the system has chaotic behavior for specific parameters and that its energy capture is influenced by parametric variation. It is shown numerically that the parameters of the SMA material, the PZT material, and the NES significantly influence the chaotic behavior and energy capture of the investigated electromechanical system.