The isotope effect on the local structure of liquid water at room temperature is studied by x-ray Raman spectroscopy. The difference between the room-temperature spectra of liquid H2O and D2O is compared to the difference spectrum between liquid H2O at 22 and 2 °C. The spectral changes between H2O and D2O can partly be attributed to structural changes similar to a temperature change, in agreement with diffraction data. Additionally, we find that isotope substitution affects the local asymmetry in the hydrogen-bonded network: hydrogen-bonding configurations are more asymmetric on the donor side for H2O than for D2O. A cluster model is used to computationally illustrate the spectral changes that arise due to the increased asymmetry, capturing all essential features in the difference spectrum. We infer from our study that quantum effects contribute to the formation of asymmetrical species in the liquid.