Hypergolic ionic liquids (HILs) are a new kind of green rocket fuels, which are used as potential replacements for toxic hydrazine derivatives in liquid bipropellants. These functional HILs can react with oxidizers and release a large amount of heat in a very short time, finally leading to ignition of the propellant system. Among them, most borohydride-rich HILs were very sensitive to water, but a few special examples displayed good hydrophobicity and remained very stable in air even after a month or more. However, the reasons behind their hydrolytic stability are unclear. In this study, several calculation methods including electrostatic potentials (ESPs), molecular orbital energy gaps, and interaction energy were used to explore the water stability of eight typical borohydride-rich Hits. The obtained results demonstrated that negatively charged anions with high absolute ESP values usually reacted more easily with positively charged water. The large molecular orbital energy gap with BPB-, BCNBCN-, CTB-, and BTB- indicates the high degree of difficulty of interactions between anions and water, leading to a better hydrolytic stability of borohydride-rich anions. During the analyses of interaction energy, the relatively water-sensitive borohydride-rich anions (BH4-, BH3CN-, etc.) generally had lower interaction energy with water than stable anions such as BPB- and BCNBCN-. Studies on their stepwise hydrolysis mechanism demonstrate that, in the case of all the reactions, the first step is the rate-determining step and high energy barrier values of anions correspond to good hydrophobicity. This study will help us understand the hydrolysis of borohydride-rich HILs and provide a guide for the development of new HILs with promising properties.