Nature has taught us fascinating strategies to design materials such that they exhibit superior and novel properties. Shells of mantis club have protein fibres arranged in a 3D helicoidal architecture that give them remarkable strength and toughness, enabling them to absorb high-impact energy. This complex architecture is now possible to replicate with the recent advances in additive manufacturing. In this paper, we used melt electrospinning to fabricate 3D polycaprolactone (PCL) fibrous design to mimic the natural helicoidal structures found in the shells of the mantis shrimp’s dactyl club. To improve the tensile deformation behavior of the structures, the surface of each layer of the samples were treated with carboxyl and amino groups. The toughness of the surface-treated helicoidal sample was found to be two times higher than the surface-treated unidirectional sample and five times higher than the helicoidal sample without surface treatment. Free amino groups (NH2) were introduced on the surface of the fibres and membrane via surface treatment to increase the interaction and adhesion among the different layers of membranes. We believe that this represents a preliminary feasibility in our attempt to mimic the 3D helicoidal architectures at small scales, and we still have room to improve further using even smaller fibre sizes of the modeled architectures. These lightweight synthetic analogue materials enabled by electrospinning as an additive manufacturing methodology would potentially display superior structural properties and functionalities such as high strength and extreme toughness.