BiVO4-Bi2O3 composite particles were synthesized by combustion synthesis (SCS) and immobilized on the ITO surface by layer-by-layer (LbL) technique. The BiVO4-Bi2O3 composite electrode was applied in the amperometric determination of atenolol (ATN) in pharmaceutical formulations and in urine using 0.25 mol L-1 NaNO3 as supporting electrolyte. A well-defined oxidation peak of ATN has been observed in 1.12 V versus Ag/AgCl (3.0 mol L-1 KCl) by cyclic voltammetry. Analytical curve presented good linearity with a correlation coefficient of 0.997 and it was obtained in the concentration range of 50.0-800 mu mol L-1 ATN with slope of 2.73 x 10(5) mu A mol(-1) L The detection limit is found to be 0.459 mu mol L-1. The proposed method was used for ATN determination in pharmaceutical formulations and urine samples and the recoveries range of 94.0 to 104%. BiVO4-Bi2O3 electrode exhibited good selectivity and repeatability, besides simplicity and low cost construction as well as stability without the need for surface renewal before each measure. (C) 2015 Elsevier B.V. All rights reserved.