Smart energy storage materials, which not only store electrochemical energy but also exhibit sensitivity to environmental stimuli, can provide novel multi-functionalities. Here, we report a smart shape memory fiber supercapacitor constituted with a highly stretchable shape memory polymer nanocomposite fiber substrate, multi-walled carbon nanotubes (MWCNT) conductive layer and pesudocapacitive polyaniline layer. Using layer by layer (LBL) technology, we first produce a densely packed MWCNT layer that serves as a well-developed conductive current collector network. Then polyaniline, as an active material, was deposited on the surface of the MWCNT layer to further promote the energy storage capability of the fibers. After the infiltration of a polyvinyl alchohol (PVA) based polymer electrolyte into the porous MWCNT and PANI layer, conductivity of ∼50S/cm and stretchability of more than 400% are obtained. The resultant shape memory polymer supercapacitors (SMPFSCs) not only possess shape memory properties, but also exhibit outstanding energy storage performance, with the best pseudo-capacitance exceeding ∼427F/cm3. Such design strategies can also be extended to other polymer substrates, and could open the door to smart (multi-functional) supercapacitor technologies.