In this work, we pioneered the development of a novel 4-aminoantipyrine loaded polylactic acid electrospun membrane for visualization and rapid detection of pentachlorophenol in water samples. The morphology, pH value, selectivity and detection sensitivity of electrospun membranes were systematically studied and optimized. The study found that the detection limit of the electrospun nanofiber polylactic acid membrane loaded with 4-aminoantipyrine was 0.4 mg/L, and the effective detection time was 0.5 h. The membranes have good stability after one month of storage in the dark at room temperature, the selectivity of 4-aminoantipyrineloaded polylactic acid electrospun membranes to other and its analogs in aqueous environment was then compared. The actual sample (including drinking water, tap water used in our lives, lake water and temporary water samples collected during production, transportation and distribution of fish) test result is negative. The fast-response electrospun nanofiber polylactic acid membrane loaded with 4-aminoantipyrine have available detection limits, simple detection methods, fast detection times, no secondary contamination of the solution to be tested, and the amount of sample required extremely small, showed great potential for materials science, environmental monitoring and food safety inspection.