Distillation is widely used for separating liquid mixtures, but its high heating demand poses challenges for achieving net‐zero emissions. This study presents an innovative approach to electrifying distillation for load adaptability and flexible operation, aligning with dynamic electricity markets driven by renewables. The approach integrates flash vapor circulation and thermal storage into the distillation to optimize power usage and capitalizes on economic opportunities from load‐flexible operation in response to fluctuating electricity pricing. A methanol/water distillation case study, using two typical electricity pricing scenarios, demonstrates that the proposed approach is more economically efficient than mechanical vapor recompression distillation, especially in lowering operational costs when the latter operates under fixed electricity pricing. However, compressor capital costs significantly impact overall costs, with sensitivity analysis examining different cost models. This approach can be applied to general distillation, allowing integration with the power sector and demand response programs, while enhancing flexibility, decarbonization, and efficiency.