High-performance capturing polar phenoxycarboxylic acids herbicides (PCAs) from water samples remains a great challenge because PCAs form salt easily and dissolve. Polyphenylene-based conjugated microporous polymers (PP-CMPs), a fascinating type of polymers, bear pi-conjugation over 3D polyphenylene scaffolds, inherent micropore, and large surface area, which are essential for capturing trace PCAs in complex samples. This work developed a novel approach to quantify trace PCAs using PP-CMPs as an efficient dispersive solid-phase extraction (d-SPE) adsorbent. The developed method based on PP-CMPs achieved high sensitivity with limits of detection of 0.55-3.84 ng L-1, satisfactory correlation coefficients (>= 0.9912), good linearity (50-10,000 ng L-1), and good precisions (2.0-9.0%). Moreover, this method was used for simultaneous monitoring of the amounts of five PCAs in environmental water samples with satisfactory spiked recoveries (86.9-101.3%). All these fact demonstrated that this new d-SPE technique based on PP-CMPs exhibited a promising potential for highly sensitive analysis of trace PCAs in complex samples.