Ab initio calculations were carried out to study the structure-property relationship of anion receptors to establish a guidance for developing advanced electrolyte for lithium-ion batteries. A group of 25 well-selected anion receptors was investigated to illustrate the impact of structural rigidity and the substitution of electron-withdrawing groups, such as F and CF3, as well as the substitution of alkoxyl groups. The calculation results showed that the fluoride affinity of an anion receptor can be reduced by the introduction of alkoxyl groups to the boron center and that the fluoride affinity increases with the substitution of electron-withdrawing groups.