Poly(vinyl alcohol) was crystallized from its aqueous solution under a steady-state flow with different conditions. Using a differential scanning calorimeter (DSC), the thermal properties of PVA precipitates obtained by the flow-induced crystallization were measured, showing a single melting peak in the DSC curve. The melting temperature of PVA crystallized depended on the rate of stirring, crystallization temperature, concentration of WA, yield of precipitates, and morphology of the crystals. Particularly, there was a closer relationship between the melting temperature and the yield of precipitates, i.e., it was through the effect on the yield of precipitates that crystallization conditions influenced the melting temperature. Generally, with certain conditions, the higher the yield of precipitates, the lower the melting temperature. Moreover, using electron microscopy, it was observed that there were some structural differences between the inner and outer sides of a PVA crystal mat round stirrer and between film-shaped and block-shaped crystals, leading to different melting temperatures.