The crystal and microstructures of the novel microfibrillar poly(vinyl alcohol) fibers (PVA fibrils) having different syndiotactic diad (S-diad) contents of 56-65% have been investigated by small- and wide-angle X-ray methods. The PVA fibrils were directly prepared from the saponification and insitu fibrillation without spinning procedure. Small-angle X-ray scattering data show that these PVA fibrils had various microvoid structures due to different stereoregularities, which was similar to those found in various natural cellulose fibers. Also, the higher the syndiotacticity was, the more regular and elongated the microvoids in PVA fibril were. This might be explained by a better alignment of PVA chains with higher syndiotacticity. To effectively orient the molecular chains of high molecular weight syndiotactic PVA fibril, a high-temperature zone drawing technique was applied. Degree of crystal orientation up to 0.991 was achieved by stretching the PVA fibril with S-diad content of 63.1% and with original degree of crystal orientation of 0.887 at around 250 degreesC close to its melting temperature. The maximum draw ratio of the PVA fibril increased with a decrease in the S-diad content, indicating that the crystal was more stable in higher syndiotactic PVA. When the same draw ratio was applied to the fibrils, higher crystal orientation was achieved for the fibrils having higher syndiotacticity. The crystallinity, the apparent lateral and longitudinal crystal sizes, and the crystal to amorphous length in long period of drawn PVA fibrils were larger in higher syndiotacticity. It turns out that PVA fibril drawn at 230 degreesC had a well-oriented lamellar structure. Moreover, dimensions of these lamellae were enlarged with increasing syndiotacticity.