Polymorphism is common in the crystalline state but rare and even controversial in the liquid or glassy state. Among molecular substances, only two are major contenders for materials that exhibit the phenomenon, including the famous case of water with its low- and high-density amorphous (LDA and HDA) ices . We report that the same phenomenon exists in another extensively hydrogen-bonded system, D-mannitol. Under the ambient pressure, D-mannitol's supercooled liquid spontaneously transforms to another amorphous phase of lower energy, larger volume (2.1%), and stronger hydrogen bonds. This transition is similar to water's HDA to LDA transition and shows the same anomaly of heat release coupled with volume expansion. In both systems, polyamorphism appears to arise from the competing demands of hydrogen bonds (loose packing) and van der Waals forces (close packing). D-mannitol is expected to play an important role as a new system for investigating polyamorphic transitions and suggests a more general occurrence of the phenomenon than the current literature indicates in systems with extensive hydrogen bonds (network bonds in general).