Display omitted •The OH stretch is mainly dependent on the local hydrogen-bonded networks.•Temperature decrease mainly leads to a structural transition from DA to DDAA.•A local statistical interpretation of the water structure is proposed. In this Letter, Raman spectroscopy is employed to study supercooled water down to a temperature of 248K at ambient pressure. Based on our interpretation of the Raman OH stretching band, decreasing temperature mainly leads to a structural transition from the single donor–single acceptor (DA) to the double donor–double acceptor (DDAA) hydrogen bonding motif. Additionally, a local statistical interpretation of the water structure is proposed, which reveals that a water molecule interacts with molecules in the first shell through various local hydrogen-bonded networks. From this, a local structure order parameter is proposed to explain the short-range order and long-range disorder.