The stability and use convenience of lipophilic phytochemicals are needed in the food or medicine fields. In this work, a new and environmentally friendly process for efficient extraction and formulation of lipophilic phytochemicals from plant had been successfully developed. A medium system consisting of water, tributyrin oil and natural amphiphilic complex particles (SPICS) was established. Under the optimal conditions of the oil/water ratio 10%, the particle concentration 2%, solid-liquid ratio 35:1 (mg/mL), ultrasound time 90 s and ultrasound power 300 W, the stable and uniform Pickering extremulsion rich in phytochemical lipophilic cannabidiol(CBD)from industrial hemp leaves was prepared. The Pickering extremulsion with the highest CBD content 1.06 mg/g was obtained, which increased 1.17-fold to the traditional Soxhlet extraction. Meanwhile, the CBD-rich Pickering extremulsion had an excellent antibacterial, antioxidant activity and cell activity with bacteriostatic diameter 7.5–18 mm, DPPH clearance rate 61.8% and cell activity of more than 80%. Besides, CBD-rich Pickering extremulsion had good bioaccessibility. In conclusion, the study provided a green, efficient and low-cost approach for simultaneous extraction and preparation of lipophilic phytochemicals, and it should provide some valuable insights for its application as nutrient or active carriers in phytochemicals field.