Herein, a novel Ti3C2Tx MXene and polyaniline nanocomposite is successfully synthesized and used for the highly efficient extraction of parabens. Polyaniline (PANI) nanofibers have formed a porous and peculiar π–π conjugated structure on hydrophilic MXene sheets, providing numerous adsorption sites for microextraction of analytes with moderate polarities such as parabens. The method is simple and sensitive, using microextraction by packed sorbent coupled with a high‐performance liquid chromatography‐ultraviolet detector. Under the optimal conditions, the method provides suitable preconcentrating factors of 28–35, ultrahigh sensitivity with low limits of detection of 0.3–0.5 µg/L, wide linearity of 0.3.0–200 µg/L with coefficients of determination ≥ 0.9983, and satisfactory precision with relative standard deviations ≤ 10.7%. The outstanding performance has been confirmed in well water and orange juice samples, with recoveries in the range of 93.1%–101.2% for water and 90.6%–103.4% for orange juice samples, respectively.