The design of hydrogel networks with tuned properties is essential for new innovative biomedical materials. Herein, poly(vinyl alcohol) and xanthan gum were used to develop hydrogels by the freeze/thaw cycles method in the presence of oxalic acid as a crosslinker. The structure and morphology of the obtained hydrogels were investigated by means of scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, and swelling behavior. The SEM analysis revealed that the surface morphology was mostly affected by the blending ratio between the two components, namely, poly(vinyl alcohol) and xanthan gum. From the swelling study, it was observed that the presence of oxalic acid influenced the hydrophilicity of blends. The hydrogels based on poly(vinyl alcohol) without xanthan gum led to structures with a smaller pore diameter, a lower swelling degree in pH 7.4 buffer solution, and a higher elastic modulus. The antimicrobial activity of the prepared hydrogels was tested and the results showed that the hydrogels conferred antibacterial activity against Gram positive bacteria (Staphylococcus aureus 25923 ATCC) and Gram negative bacteria (Escherichia coli 25922 ATCC).