Polyvinyl alcohol (PVA) fibers were prepared using PVA with different degree of polymerization (DP) under the same wet spinning process. The effect of the DP of PVA on the structures and properties of PVA and PVA fibers were studied by using nuclear magnetic resonance hydrogen spectroscopy (1H‐NMR), Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), differential scanning calorimeter (DSC), thermo gravimetric analysis (TGA), and environmental scanning electron microscope (ESEM). The results showed that DP had little effect on the crystallinity and tacticity of PVA, but had a positive effect on melting temperature, and initial decomposition temperature of PVAs. The hot drawing ratio determined by the spinning process where the PVA fibers could be continuously collected without breaking. The drawing ratio was decreased with an increase of DP, resulting in an increase of the final fiber diameter. The PVA fibers with medium DP and medium size demonstrated high strength and high modulus, but relatively low breaking elongation. It suggested that high DP of PVA was not a guarantee of high strength and high modulus PVA fibers, but rather a primary structure factor. The fiber performance was determined by a comprehensive effect combining a variety of factors including polymer properties and spinning conditions. It provided a guideline for PVA fiber manufacture that the PVAs with different DP require different spinning processes to obtain optimal fiber performance.