A chrome-free tanning process of an ecological leather is characterized by a TWS+sodium lignosulfonate+TWLZ ternary tanning process system. The sodium lignosulfonate added can not only have a fixation effect on a TWS tanning agent to make the TWS tanning not undergo detanning at a low pH, but also significantly improve the uniformity of distribution of a TWLZ tanning agent in a hide/skin and promote the formation of a stable cross-linked network structure by the TWLZ tanning agent in a collagen fiber, which effectively overcomes the defects of tanning performance of the existing tanning systems to obtain a leather with uniform and sufficient tanning, a high isoelectric point, a strong electropositivity, excellent absorption for post-tanning chemicals, and a prominent softness, and gives a leather a wide use range and a high quality.