Two types of alpha-Fe2O3 nanostructures were synthesized under hydrothermal conditions in the presence of glycerol. Urchin-like alpha-Fe2O3 with limited (001) plane exposure and flower-like alpha-Fe2O3 with a high degree of (001) plane exposure were used to modify the surfaces of screen-printed electrodes (SPEs), which were then employed in electrochemical Cr(VI) detection. Linear sweep voltammetric results indicate that the high exposure of the (001) plane could result in a high current response toward Cr(VI) reduction due to the high adsorption capacity induced by doubly and triply coordinated hydroxyl groups on the surface of alpha-Fe2O3. The modified SPE had a linear response to Cr(VI) in the 5-3000 mu g/L concentration range with a detection limit of 1.17 mu g/L.