The Electrochemical behaviors of Daunorubicin hydrochloride, and the interactions between Daunorubicin hydrochloride and BSA, were studied in this paper, with Linear sweep voltammetry and Cyclic voltammety methods. The results showed that, there was a reductive peak at E=-0.66V in the Linear sweep voltammetry of Daunorubicin hydrochloride, on condition of 0.1 mol·L^-1Na₂SO₄, pH 8.5B-R buffer solution. After BSA was introduced, the system peak current reduced. There was a maximal system peak current Δip″, when the concentration of Daunorubicin hydrochloride was 5.0×10^-5 mol·L^-1. At the range of 5.0×10^-8 mol·L^-1-1.0×10^-4 mol·L^-1 of the concentration of BSA, it existed a good linear relation between the reduced valve of the peak current of Daunorubicin hydrochloride and the concentration of BSA. This method can be used in the detection of the concentration of BSA.