The invention relates to a preparation method of chromium-free pickled leather, which can uniformly expand and be loosened properly, is beneficial to permeation and combination of tannins and dyes, and ensures that finished leather is soft and flat and fine in grain surface. Specifically, the following procedures are sequentially carried out: fur soaking, fleshing, pre-degreasing, enzyme depilating, alkali soaking, leather peeling, dealkalizing, degreasing and softening, pickling and pickled leather production, wherein the alkali soaking comprises the following steps: putting depilated leatherinto a rotary drum, controlling the liquid ratio to be 1.2-1.5, adding 0.2-0.5% of a penetrant and 0.5-0.8% of sodium hydrogen sulfide, and carrying out low-speed rotary drum treatment for 10-15 minutes; then, stopping operation of the drum and supplying water to adjust the pH value to be 7-8, sequentially adding 0.8%-1.0% of xonotlite fiber particles, 1.5%-3.0% of slaked lime and 0.8%-1.0% of alkaline leaching enzyme, performing low-speed rotary drum treatment at a low speed for 30-45 minutes, inspecting the leather, and washing the leather with water and discharging the leather from the drum after the expansion degree meets the requirement.