In recent years there have been many papers that considered the pyroelectric effect in the investigations of thermo-mechanical coupling of piezoelectric ceramics serving in non-uniform thermal environment, particularly with extensive applications of ultrafast heating technologies (e.g., laser burst, laser ablation, etc.) in micro-machining of piezoelectric structures (e.g., piezoelectric sensor/actuator/generator/energy harvester, etc.). However, in such conditions, the existing piezoelectric thermoelasticity theories will not be applicable due to the lack of consideration of the memory-dependence feature in the constitutive relations and heat transport equation. To further refine the piezoelectric thermoelasticity models, present study develops a new theoretical model of generalized piezoelectric thermoelasticity which fully account for fractional order strain and heat conduction. By establishing constitutive equations within the extended thermodynamic framework, the governing equations are derived. In the aspect of application, the transient thermo-electromechanical responses of multi-layered piezoelectric laminated composite structure with non-idealized interfacial conditions is investigated. The effects of material constants ratio and fractional order parameters of each layer on structural responses are evaluated and summarized to offer some new insights and guidelines on the strength design, thermal protection, and vibration control of multi-layered piezoelectric laminated composite structure under ultrafast heating condition.