Tanning is a magical procedure for the transformation from raw hides to leather. Chrome tanning agents play a leading role in leather production due to excellent penetration and comprehensive performance. Whereas the restrictions on waste emission contain Cr increase around the world in recent years, it’s necessary to develop and promote chrome-free tanning agents. Nature polysaccharide biomass materials allow for adjustable molecular size, abundant functional groups and excellent penetration, but they show insufficient tanning. A large amount of metal ions in nanomaterials contribute to firm crosslinks with collagen fibers and poor permeability of nanomaterials. Therefore, if polysaccharide biomass materials can be integrated with nanomaterials, the composite could take advantages of these two resources to replace chrome tanning agents, thus achieving environmentally friendly chrome-free tanning in the future. In this review, latest progress about chrome free tanning agents is summarized, especially for the investigation and application of polysaccharide (like starch and cellulose) and nano(like montmorillonite and hydrotalcite) series tanning agents. Accordingly, the current issues and future trends of chrome-free leather tanning agents were discussed.