This review is designed to foster the discussion regarding the viability of postcombustion CO2 capture by water-lean solvents, by separating fact from fiction for both skeptics and advocates. We highlight the unique physical and thermodynamic properties of notable water-lean solvents, with a discussion of how such properties could translate to efficiency gains compared to aqueous amines. The scope of this review ranges from the purely fundamental molecular-level processes that govern solvent behavior to bench-scale testing, through process engineering and projections of process performance and cost. Key discussions of higher than expected CO2 mass transfer, water tolerance, and compatibility with current infrastructure are presented along with current limitations and suggested areas where further solvent development is needed. We conclude with an outlook of the status of the field and assess the viability of water-lean solvents for postcombustion CO2 capture.