Phase-resolved sum-frequency generation measurements combined with molecular dynamics simulations are employed to study the effect of temperature on the molecular arrangement of water on the basal face of ice. The topmost monolayer, interrogated through its nonhydrogen-bonded, free O-H stretch peak, exhibits a maximum in surface H-bond density around 200 K. This maximum results from two competing effects: above 200 K, thermal fluctuations cause the breaking of H bonds; below 200 K, the formation of bulklike crystalline interfacial structures leads to H-bond breaking. Knowledge of the surface structure of ice is critical for understanding reactions occurring on ice surfaces and ice nucleation.