The polymer, poly(vinyferrocenium) (PVF+) modified electrode was developed as the first time herein for the improved electrochemical sensing of DNA based on the oxidation signals of polymer and guanine. The morphologies of polymer film and DNA immobilized polymer film were examined using scanning electron microscope (SEM). The electrochemical behavior of polymer modified electrode was investigated by using cyclic voltammetry (CV) and differential pulse voltametry (DPV) in the absence/presence of DNA. Experimental parameters, such as the polymeric film thickness, the DNA immobilization time, the concentration of buffer solution, pH and DNA concentration were examined in order to obtain more sensitive and selective electrochemical signals. After optimization studies, DNA hybridization was also investigated.