An improvement of selectivity for electrochemical detection of dopamine (DA) with differential pulse voltammetry is achieved by covalently modifying a glassy carbon electrode (GCE) with O-carboxymethylchitosan (OCMCS). The amphiphilic chitosan provides electrostatic accumulation of DA onto the electrode surface. In a phosphate buffer solution (pH 6.0), a pair of well-defined reversible redox waves of DA was observed at the OCMCS/GCE with a Δ E p of 52 mV. The anodic peak current obtained from the differential pulse voltammetry of dopamine was linearly dependent on its concentration in the range of 6.0 × 10 -8 to 7.0 × 10 -6 M, with a correlation coefficient of 0.998. The detection limit (S/N = 3) was found to be 1.5 × 10 -9 M. The modified electrode had been applied to the determination of DA in human serum samples with satisfactory results.