A series of novel organic-ligand-doped sodium bis(oxalate)-borate complexes, including sodium bis[salicylato(2-)]-borate (NBSB), sodium[salicylato benzenediol]borate (NBDSB), sodium bis[oxalate]-borate (NBOB) and its derivatives NBOB(C2H2O4)0.2, NBOB(C7H4O3)0.2, NBOB(C7H4O3)0.6, NBOB(C6H6O2)0.15 and NBOB(C6H6O2)0.3 fabricated by solid-state reaction are firstly developed as new-type electrolytes for sodium ion batteries. These resulting sodium boron salts possess good solubility in an abroad range of organic solvents (such as PC, AN, DMF, PC + AN, PC + DMF), tailored thermal stability from 300 to 353 °C, improved ion conductivity (>1 × 10−3 S cm−1), environmental friendliness and low cost. Therefore, we believe that these new-type sodium boron salts show great potential as a new class of electrolyte for high-performance sodium ion batteries.