© 2021 Elsevier LtdTendon and ligament impairments are among the most familiar injuries of the knee with acute or chronic pain conditions. The defects of anterior cruciate ligament (ACL) stay a known clinical problem. In the present study, the electrospinning method was used to fabricate 10wt.%PCL/(1, 3, 5)wt.%Chitosan (CS) appropriate and biocompatible scaffolds with a similar connective ligament geometry and structure. 10wt.%PCL/3wt.%CS demonstrated higher tensile strength value (0.58854 MPa) than other scaffolds in the tensile test. Moreover, 10wt.%PCL/3wt.%CS scaffolds had high mesenchymal stem cells (MSCs) viability value for all incubation periods. Swelling and degradation behaviours of the ligament-like scaffolds were examined in vitro for 15 days. Results reported that the highest swelling ratio was observed with CS addition for 10wt.%PCL/5wt.%CS scaffolds which value nearly reached to the 270% ratio. Scanning electron microscope proved the geometry of the scaffolds, which were suitable for ligament-like tissue. Attachment of MSCs on the scaffolds proved the network-like structure of the cells on the scaffolds.