Cell therapy and tissue engineering attract increasing attention as a potential approach for cardiac repair. Although a plethora of interesting concepts in the emerging field of cardiac stem cell-based tissue engineering are reported, there are still challenges that this field needs to overcome to achieve therapeutic translation into the clinical praxis. Engineering biomaterial scaffolds that facilitate stem cell engraftment, survival and homing are crucial for successful cellular cardiomyoplasty after myocardial infarction (MI). In this study we investigate for the first time the cellular response of Wharton's jelly (WJ) Mesenchymal Stem Cells (MSCs) on a copolymeric material comprising chitosan (CS) and poly(ε-caprolactone) (PCL). First we synthesize a copolymer consisting of poly(ε-caprolactone) grafted on a chemically modified chitosan-backbone (CS-g-PCL). Furthermore, we investigate the morphology, viability and proliferation of WJMSCs on material coatings and examine the cellular response from different donors. Our results show strong cell adhesion on the CS-g- PCL material surface from the first hours in culture, and a proliferation increase after 3 and 7 days. These findings support the potential use of our proposed cell-material combination in myocardium tissue engineering.