Tissue engineering has shown a remarkable result in medical applications. Further exploration, these multidisciplinary fields are also given a possibility as an alternative medication for intervertebral disc (IVD) degeneration. Focusing on the annulus fibrous repair, to improve the mechanical properties of biomaterials, a composite made of chitosan and polycaprolactone (PCL) was developed in this present study. Due to its tuneable properties, the electrospinning-based method was used in the experiment to create the chitosan/PCL composite. Varies concentration of PCL (11, 12, and 13 wt%) and a different ratio of precursors chitosan to PCL (1:1; 1:3; 1:5) were used to optimize the composition of natural and synthetic polymer in the composite nanofibers. The obtained nanofibers were then characterized using Scanning Electron Microscopy (SEM) to observe the morphology, swelling test, Fourier Transform Infrared (FTIR) spectroscopy, and Differential Scanning Calorimetry (DSC). The results show that the increasing concentration and composition of PCL could form the more homogeneous and larger diameter of nanofiber with fewer beads compare to the lower composition of PCL nanofiber. Meanwhile, the swelling percentage decreases by increasing the amount of PCL. FTIR results also show that all samples of composite nanofibers contain both chitosan and PCL.