Polyvinyl alcohol is difficult to form fiber-like crystal through inducing by shear flow, and a fiber containing high amount carbon nanotubes (CNTs) is also difficult to be prepared by conventional spinning processes. In this paper, the facile and novel approach for fabricating syndiotactic polyvinyl alcohol (s-PVA) fiber-like materials containing high amount single-walled carbon nanotubes (SWNTs) under shear flow field is offered. The mixture of different amount of SWNTs and s-PVA dilute aqueous solution was stirred with a stainless steel cylindrical stirrer at certain rotational speed in a plastic tube. During the stirring period, the fibrous crystals gradually formed around the stirrer, then were removed and kept in methanol, and finally dried in air to obtain dried fiber. The process of the fiber formation was observed by high-definition camera, the fiber morphology was measured by TEM, SEM and polarized optical microscope, and the amount of SWNTs in the fiber was determined by TGA. The results show that the fiber consists of many well-oriented fibrils that are composed of the bundles wrapped by the s-PVA nanocrystals, and contains SWNTs up to 22 wt% when the SWNTs is 10 wt% based on s-PVA in the mixture solution.