The beneficial effects of graduated compression stockings (GCS) in prophylaxis and treatment of venous disorders of human lower extremity have been recognized. However, their pressure functional performances are variable and unstable in practical applications, and the exact mechanisms of action remain controversial. Direct surface pressure measurements and indirect material properties testing are not enough for fully understanding the interaction between stocking and leg. A three dimensional (3D) biomechanical mathematical model for numerically simulating the interaction between leg and GCS in dynamic wear was developed based on the actual geometry of the female leg obtained from 3D reconstruction of MR images and the real size and mechanical properties of the compression stocking prototype. The biomechanical solid leg model consists of bones and soft tissues, and an orthotropic shell model is built for the stocking hose. The dynamic putting-on process is simulated by defining the contact of finite relative sliding between the two objects. The surface pressure magnitude and distribution along the different height levels of the leg and stress profiles of stockings were simulated. As well, their dynamic alterations with time processing were quantitatively analyzed. Through validation, the simulated results showed a reasonable agreement with the experimental measurements, and the simulated pressure gradient distribution from the ankle to the thigh (100:67:30) accorded with the advised criterion by the European committee for standardization. The developed model can be used to predict and visualize the dynamic pressure and stress performances exerted by compression stocking in wear, and to optimize the material mechanical properties in stocking design, thus, helping us understand mechanisms of compression action and improving medical functions of GCS.