In this study, bipolar membrane electrodialysis was proposed to directly convert L-ornithine monohydrochloride to L-ornithine. The stack configuration was optimized in the BP-A (BP, bipolar membrane; A, anion exchange membrane) configuration with the Cl− ion migration through the anion exchange membrane rather than the BP-A-C (C, cation exchange membrane) and the BP-C configurations with the L-ornithine+ ion migration through the cation exchange membrane. Both the conversion ratio and current efficiency follow BP-A > BP-A-C > BP-C, and the energy consumption follows BP-A < BP-A-C < BP-C. Additionally, the voltage drop across the membrane stack (two repeating units) and the feed concentration were optimized as 7.5 V and 0.50 mol/L, respectively, due to the low value of the sum of H+ ions leakage (from the acid compartment to the base compartment) and OH− ions migration (from the base compartment to the acid compartment) through the anion exchange membrane. As a result, high conversion ratio (96.1%), high current efficiency (95.5%) and low energy consumption (0.31 kWh/kg L-ornithine) can be achieved. Therefore, bipolar membrane electrodialysis is an efficient, low energy consumption and environmentally friendly method to directly convert L-ornithine monohydrochloride to L-ornithine.