The recent advances in electrospinning have resulted in technologies facilitating easy drug entrapment, obtaining high surface area and thereby higher drug loading and release efficacy, burst control as well as the specific morphology which could be controlled according to the desired requirement. The present study focused on the fabrication of collagen/poly(-isopropyl acrylamide)/chitosan complex with incorporated 5-fluorouracil, an anticancer drug by the method of electrospinning. The effect of chitosan on the fiber morphology and release kinetics was analyzed by varying its concentration. The release kinetics showed that the increase in chitosan concentration delayed the release of the drug from the fiber network. Nano hydroxyapatite was added to the fiber matrix in order to impart bioactivity, which was confirmed by studies in simulated body fluid. The addition of poly(-isopropyl acrylamide) increased the blood compatibility of the prepared model. Thus, the model prepared to can find potential application in the field of cancer therapy as a drug-delivery agent in post-surgical treatment of cancer and as blood contacting biomaterial.