High-performance chrome-free leather production is currently one of the most concerning needs to warrant the sustainable development of the leather industry due to the serious chrome pollution. Driven by these research challenges, this work explores using biobased polymeric dyes (BPDs) based on dialdehyde starch and reactive small-molecule dye (reactive red 180, RD-180) as novel dyeing agents for leather tanned using a chrome-free, biomass-derived aldehyde tanning agent (BAT). FTIR,1H NMR, XPS, and UV-visible spectrometry analyses indicated that a Schiff base structure was generated between the aldehyde group of dialdehyde starch (DST) and the amino group of RD-180, resulting in the successful load of RD-180 on DST to produce BPD. The BPD could first penetrate the BAT-tanned leather efficiently and then be deposited on the leather matrix, thus exhibiting a high uptake ratio. Compared with the crust leathers prepared using a conventional anionic dye (CAD), dyeing, and RD-180 dyeing, the BPD-dyed crust leather not only had better coloring uniformity and fastness but it also showed a higher tensile strength, elongation at break, and fullness. These data suggest that BPD has the potential to be used as a novel sustainable polymeric dye for the high-performance dyeing of organically tanned chrome-free leather, which is paramount to ensuring and promoting the sustainable development of the leather industry.