Electrospun fiber scaffolds has made a huge progress in tissue engineering applications owing to their continuous morphology with variable chemical, physical, and biological properties. In this review paper, we reviewed the electrospinning technique, its processing parameters and characterizations involved. A focus on shape memory poly (glycerol sebacate) (PGS)-based electrospun fiber scaffolds for tissue engineering field was explored. The stimuli responsive PGS scaffold has gained much attention due to its ability to self-expanding, self-deploying, or self-fitting. Herein, the electrospinning of shape memory PGS-based scaffolds, particularly their processing parameters, properties, and characterizations have been reviewed. Besides, other issues concerning the technology constraints, challenges, and future directions are also discussed.