Poly(vinyl alcohol) (PVA) foams were prepared using a green lyophilization process without the use of foaming agents. PVA solutions with contents of CNCs (1 – 4 wt%) were prepared at two different freezing temperatures (−20 and −186 °C). With the addition of CNCs, moisture uptake of the CNC-PVA foams prepared at two freezing temperatures was lower than the neat PVA foams. With increasing CNC contents, no significant change of the moisture uptake could be observed for both types of the foams. Similar values of the moisture uptake could be found from both foams frozen at −20 and −186 °C. Scanning electron microscope measurements revealed the aligned-porous-structure of the foams frozen at −186 °C along with the ice growth direction while large and elongated pores were observed from the foams with the lower freezing temperature. These unique features of the foams prepared by a freeze-drying technique could be controlled by changing the freezing temperature, and these foams could be useful for specific applications such as tissue engineering scaffolds, thermal insulators or filters.