The anterior cruciate ligament rupture is one of the most common sport injuries. Due to ligaments’ poor healing capacity, surgical intervention is often required. Nowadays, these injuries are managed using replacement autografts or to a lesser extent using artificial ligaments. With the expansion of tissue engineering, more recent researches focus on the development of biodegradable structures that could allow graft functioning while enhancing host integration. The main challenge is to develop a structure that gradually loses its mechanical properties when at the same time the neo-ligament gains in solidity. Mechanical behavior and reconstruction of natural tissue are the two key points for such a successful device. This article evaluates the mechanical consistency of poly(ε-caprolactone) fibers bundles grafted with sodium polystyrene sulfonate, as a candidate for ligament prosthesis. In order to be medically used, PCL fibers need to cope with multiple steps before implantation including extensive washings, knitting, grafting and sterilization processes. The evolution of mechanical properties at each step of the elaboration process has been investigated. The results show that PCL bundles have the same visco-elastic behavior than the native ACL. Nevertheless, when undergoing physical treatments such as ionizing radiations, like UV or β-rays, the material endures a hardening, increasing its stiffness but also its fragility. At this opposite, the thermal radical grafting acts like an annealing step, increasing significantly the elasticity of the PCL fibers. With this chemical treatment, the stiffness is decreasing, leading to higher energy dissipation. Added to the observation of the structure of the material, this demonstrates the possibility of the PCL to modulate it microstructure. In case of orthopedic prosthesis, the need of such a construct is strongly required to avoid distension of the future prosthesis and to restore good knee stabilization, showing the promising future of PCL ligament prosthesis.