The electrochemical stability of room-temperature ionic liquids (RTILs) is a critical design consideration for electrochemical applications. An electrochemical solvent, such as the electrolyte in a lithium-ion battery or supercapacitor, must support the voltage in which the device operates. In this talk, we present the insights into the electrochemical stability of RTILs obtained using a novel combination of first principles density functional theory calculations and classical molecular dynamics simulations. We show that while simple gas phase models can be used to reveal broad qualitative trends in electrochemical stability, quantitative accuracy can be achieved only by explicitly modeling all inter-ion interactions in the liquid. Additionally, detailed investigations into the six room-temperature ionic liquids (ILs) formed from a combination of two common cations, 1-butyl-3-methylimidazolium (BMIM) and N ,N -propylmethylpyrrolidinium (P13), and three common anions, PF6 , BF4 , and bis(trifl uoromethylsulfonyl)imide (TFSI) provide surprising evidence of possible cation anodic instability, particularly in BMIM-based ILs.