Completely isotactic polyacrylonitrile (meso/meso triad >99%) has been synthesized successfully by radiation-induced inclusion polymerization of acrylonitrile in urea canals. The long-lived nature of the growing radical species and the linear dependence of molecular weight on conversion were observed. The molecular weight distribution of product polymers was relatively narrow (<1.5). The results indicate that the dual control of the molecular weight and the tacticity for inclusion polymerization of acrylonitrile in urea canals is achieved. In addition, the effect of experimental factors of inclusion polymerization on the isotacticity of product polymers was investigated. It is found that to ensure completely isotactic polyacrylonitrile, the following conditions should be met simultaneously: (1) acrylonitrile monomers are included in urea canals totally before γ-ray irradiation, (2) the temperature at the chain propagation step is lower than −90 °C, and (3) the heat of polymerization is removed effectively.