Abstract: As an emerging water treatment technology, photocatalysis conforms to the development concepts of green, circular and low-carbon. However, it has poor selectivity for low-concentration pollutants, and the recovery of traditional TiO₂ photocatalysts is relatively difficult. By combining macromolecular self-assembly technology, photocatalysis and molecular imprinting technology, photocatalytic molecularly imprinted composite nanoparticles with adhesive properties were modified on the surface of glass fibers. These multifunctional glass fibers integrated specific molecular enrichment and efficient photocatalytic degradation, achieving highly selective catalytic degradation of low-concentration organic pollutant p-nitrophenol (PNP). Moreover, the good adhesion of the composite nanoparticles also greatly improved the cyclic stability of the photocatalyst. The prepared p-nitrophenol@titanium dioxide/polymer composite nanoparticles (PNP@TiO₂/PAVD NPs) had an irregular spherical shape with a diameter of approximately 50 nm, and the removal rate of PNP reached as high as 97.57%, indicating good selectivity for the catalytic degradation of PNP. Our research not only realized the efficient enrichment and degradation of target water pollutants, but also provided a convenient method for the separation and recovery of photocatalysts.