The purpose of this study was to search for a suitable material for the tissue engineering of anterior cruciate ligaments (ACLs) through studying the cell behaviors of ACL cells on materials. Two biodegradable material, chitosan and polycaprolactone (PCL), were included in the first part. We not only evaluated the biocompatibility of ACL cells on these materials but also the potentiality of ACL cells synthesized extracellular matrix (ECM) on these materials. The results indicated ACL cells on chitosan expressed higher level of transforming growth factor β (TGF β) and collagen type III gene than that of ACL cells did on PCL. However, ACL cells presented round cells shape and did not proliferate well on chitosan. In order to overcome this drawback, in the second part, we introduced PCL into chitosan to create chitosan/PCL blended materials and we expected PCL could promote cells to adhere on the materials. The results showed the number of cells adhering on the blended material increased as the PCL content increased in the blends and the behaviors of gene expression of ACL cells were closely related to the cell shape. Therefore, we found using blended materials could make cells be a beneficial shape for proliferating and synthesizing ECM. In the third part, the chitosan/PCL blends were applied to the different cell types. In the study of human bone marrow mesenchymal stem cells (hBMSCs), the results revealed chitosan/PCL blends could induce hBMSCs into chondrogenesis through the alteration of cell shape. In the study of human keratinocyte cell line (HaCaT) and human fibroblast cell line (Hs68) co-culture system, the results illustrated chitosan/PCL blends affected the cell distribution by controlling cells to present different adherent behaviors on the material. According to our studies, we propose a new concept for the biomaterial selection of tissue engineering. Using blended material could simultaneously control cells toachieve proliferation and phenotypic function.