In the present work,it was found that aqueous solution of a hydrophilic ionic liquid (IL),1-butyl-3-methylimidazolium dicyanamide ([C4mim][N(CN)2]),could be separated into an aqueous two-phase system (ATPS) by inorganic salts such as K2HPO4 and K3PO4.The top phase is IL-rich,while the bottom phase is phosphate-rich.It was shown that 82.7%-100% bovine serum albumin (BSA) could be enriched into the top phase and almost quantitative saccharides (arabinose,glucose,sucrose,raffinose or dextran) were preferentially extracted into the bottom phase in a single-step extraction by [C4mim][N(CN)2] + K2HPO4 ATPS.The extraction efficiency of BSA from the aqueous saccharide solutions was influenced by the molecular structure of saccharides.The conductivity,dynamic light scattering (DLS) and transmission electron microscopy (TEM) were combined to investigate the microstructure of the IL-rich top phase and the possible mechanism for the selective separation.It is suggested that the formation of the IL aggregate and the IL aggregate-BSA complex plays a significant role in the separation of BSA from aqueous saccharide solutions.This is the first example for the selective separation by ILs-based ATPSs.It is expected that these findings would have potential applications in bio-analysis,separation,and IL recycle.