This study investigates the capacity of albumin-grafted biomaterials as tissue engineering scaffolds to regenerate cartilaginous components. Porcine knee chondrocytes were seeded and cultivated in porous ternary matrix consisting of polyethylene oxide, chitin, and chitosan with surface albumin. The results revealed that the quantity of albumin did not affect the viability of porcine knee chondrocytes in the constructs. However, a high grafting concentration of albumin favored the adhesion of porcine knee chondrocytes on the scaffolding pore surface. After cultivation over 4 weeks, an increase in the concentration of albumin enhanced the quantities of porcine knee chondrocytes, glycosaminoglycans, and collagen in the constructs. The histological staining of porcine knee chondrocytes showed an active chondrocytic growth in the albumin-grafted constructs. In addition, the safranin-O staining indicated that the surface albumin could stabilize the secretion of glycosaminoglycans. Moreover, the immunochemical staining against type II collagen exhibited a regular production of collagen by phenotypic porcine knee chondrocytes in the constructs. Albumin-grafted polyethylene oxide/chitin/chitosan scaffolds can be a promising biomimetic substrate in neocartilage formation.