Chiral amines are highly coveted within the fine‐chemical industry and sustainable synthetic methodologies for their production are of great value. By harnessing the chirality present in cellulose‐derived (–)‐levoglucosenone (LGO), several bio‐based sp³‐rich amines containing up to four chiral centres have been readily prepared under aqueous conditions without using any catalysts, ligands, auxiliaries or resolutions.