<p>The investigation on the transient thermo-electro-mechanical impact behavior of multilayered piezoelectric composites is crucial to control vibration and manage heat for ultrafast-heated piezoelectric structures. However, the memory-dependent effect in the electron–phonon two-temperature in such condition has not yet been studied. To deal with such deficiency, the present work aims to establish the L-S piezoelectric thermoelasticity based on non-singular fractional electron–phonon two-temperature model with Atangana–Baleanu (AB) and Tempered-Caputo (TC) definitions. The proposed model is applied to investigate thermo-electro-mechanical transient impact responses of the heat-shock multi-laminated piezoelectric composites structure with imperfect interfaces via Laplace transformation techniques. Dimensionless results reveal that the new memory-dependent parameters in fractional electro-phonon two-temperature model and different material ratios maximally lift the ability of capturing electric potential, lower harmful temperature/stress (deformation) responses and reduce the heat wave propagation speed in structure or imperfect interfaces. The achieved results in this work offer the new basis of optimization design of piezoelectric-thermoelastic coupling behavior for piezoelectric structures in the ultrafast heating condition.</p>