A polyacrylonitrile fiber catalyst with high polar surface micro‐environment (C‐PANF‐Na) was conveniently synthesized and characterized by elemental analysis, Fourier‐transfer infrared spectroscopy, UV–vis spectroscopy, scanning electron microscopy, X‐ray diffraction, and breaking strength test. The catalytic performance of the fiber was tested by Henry reaction and Gewald reaction in water and favorable results were obtained in terms of high yields, mild conditions, extensive applicability, superior catalytic recyclability, and renewability. It also has advantages of easy preparation, high functional degree, good stability in acid and base, high strength, and good flexibility, and so on. In addition, a high solvent selectivity phenomenon was found in this catalytic system and the reason was explained by proposing a high polar micro‐environment effect. Furthermore, the fiber catalyst performed well in scaled‐up experiment and flow chemistry experiment, which shows tremendous potential in industrial catalyst as an ideal material for packed bed. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45992.