The electrochemical behavior of pirarubicin(THP) and its interaction with DNA at a Co/GC modified electrode was studied by linear sweep and cyclic voltammetries. In a 0.01 mol/L B-R buffer solution(pH=7.0), the reaction of DNA with THP formed an electrochemical nonactive complex, resulting in a decrease in the THP equilibrium concentration and its reduction current. The composition of the complex was THP∶DNA=2∶1. The combining constant is 2.73×1010. The electrode reaction rate constant ks and the electron transfer coefficient α are 1.32 s-1 and 0.56, respectively. The decrease in the peak current was proportional to the DNA concentration and was used to determine the DNA concentration. The experiment of XPS showed that Co was surely implanted into the surface of GCE(glassy carbon electrode) and the implanted Co at GCE can improve the electrocatalytic activity.