The syndiotacticity-rich (syndiotactic diad content of 57-65%) high molecular weight (number-average degree of polymerization of 4500-20 000) poly(vinyl alcohol) (PVA) microfibrillar fiber was directly produced via the saponification reaction of poly(vinyl pivalate) (PVPi) by controlling structural factors such as molecular weight and stereoregularity of PVA chains, and appetence between PVA and solvent without existing spinning procedures. By examining and observing the changes of flow birefringence, shear viscosity of reaction solution, degree of saponification, and shape of reaction product during the saponification reaction, the following novel formation mechanism of high strength microfibrillar PVA fiber is proposed. As PVPi converts into syndiotactic PVA by means of saponification using saponifying agents containing water, an oriented gel structure appears first by the interaction between water and hydroxyl groups of syndiotactic PVA formed during the saponification reaction, and then the microfibrillar structure is formed by the collapse of water-PVA interbridges and the resultant chain packing between syndiotactic PVA molecules. The larger the syndiotacticities of both PVPi and PVA, the higher the molecular orientation and the smaller the hydroxyl groups in P(VPi-VA) copolymer needed for in situ fibrillation. The well oriented microfibrillar PVA fiber prepared by such a manner had irregular cross-sections, needle-point-like ends, accumulated ultrafine microfibril structure.