Using combined theoretical and experimental approaches, we demonstrate that the bond orientation of water at the water-vapor interface depends markedly on the water isotope (H-D) composition. While the interfacial water structures of H(2)O and D(2)O are indistinguishable, the intramolecular symmetry breaking in HDO is directly reflected at the surface: the OD bonds preferably orient down towards the bulk water, whereas the OH bond tends to orient up into the vapor phase. Path integral molecular dynamics simulations show good agreement with surface-specific sum-frequency generation (SFG) spectroscopy results, revealing that the distinct interfacial bond orientations originate from nuclear quantum effects. The enhanced localization of the heavier D atom leads to stronger hydrogen bonds, giving rise to OD bonds pointing down into the bulk.