Abstract: Thermoplastic shape memory composite materials, possessing the excellent mechanical performances, thermal stability and unique deformation abilities, exhibit the widely application prospect in fields of biomedicine, electrical devices and aerospace structures. Additionally, poly(aryl ether ketone) (PAEK), as a kind of high-performance engineering plastic, exhibit the great mechanical properties, thermal stability and chemical resistance, which has been an appropriate substitute of metal in aerospace structures, due to the low-density and easy-processing. In the paper, a series of PAEKs were synthesized via a stepwise polymerization reaction, and the construction of alternative flexible-rigid structures in molecular main chain endows the excellent shape memory behaviors. Besides, carbon fiber fabric (CFF) was integrated into PAEK matrix to fabricate the composites, and the effect of CFF’s content, layers and arrangements on mechanical properties (Tensile strength up to 347.2 MPa, Young’s modulus up to 4.4 GPa) and shape memory abilities (Shape recovery ratio up to 99.9%) of the composites was investigated. Furthermore, we fabricated the multi-shape memory PAEK material through compounding the various PAEKs with programmable transition temperature, and prepared the corresponding CFF/PAEK composites. The composites exhibit the unique triple-shape memory behaviors, which possess the widely applications in aerospace area.