Water existing in the vicinity of polyelectrolytes exhibits unique structural properties, which demonstrate key roles in chemistry, biology, and geoscience. In this study, X-ray absorption and emission spectroscopy was employed to observe the local hydrogen-bonding structure of water confined in a charged polyelectrolyte brush. Even at room temperature, a majority of the water molecules confined in the polyelectrolyte brush exhibited one type of hydrogen-bonding configuration: a slightly distorted, albeit ordered, configuration. The findings from this study provide new insight in terms of the correlation between the function and local structure of water at the interface of biological materials under physiological conditions.