This study investigated the direct citric acid hydrolysis extraction method to optimize phytosterols extraction from hickory husk. Single factor experiments followed by a three-level three-factor Box-Behnken experiments were performed. The optimal extraction parameters were determined as: pH of 2.0, liquid-to-solid ratio of 17.12: 1 mL/g, and temperature of 55.81 °C. Practical experiments were carried out in triplicate, and subsequently yielded phytosterols of 912.452 ± 17.452 μg/g DW, in good consistence with the predicted extraction yield of 902.874 μg/g DW. The conductivity of the extract was also found to play effective role under direct citric acid hydrolysis and recorded 36.30 ± 1.08 μs/cm at optimum extraction condition. β-Sitosterol stigmasterol, campsterol, ergosterol and lupeol were detected as main PSs and triterpenoids in hickory husk using UPLC-Triple-TOF/MS. Finally, the comparison between direct hydrolysis extraction and traditional solvent extraction showed that this new method was more effective and eco-friendlier to extract both free and conjugated phytosterols.