Poly(vinylferrocenium) (PVF+) modified gold (Au) electrode was developed in this study for the electrochemical sensing of deoxyribonucleic acid (DNA) hybridization based on the oxidation signals of polymer and guanine, and also for the electrochemical investigation of interaction of anticancer drug, mitomycin C (MC) and DNA immobilized onto PVF+ modified Au electrode. PVF+ modified Au electrode was prepared by electrooxidation of poly(vinylferrocene) PVF at +0.7 V versus Ag/AgCl reference electrode. The polymer modified electrode and DNA immobilized polymer modified electrode were characterized by X-ray photoelectron (XPS), Fourier transform infrared-attenuated total reflentance (FTIR-ATR) and alternating current (AC) impedance spectroscopy. For application studies, differential pulse voltammetry (DPV) technique was used.