Ether-based acyclic solvents have a tendency to confine positively charged atoms, forming structures called podands. Due to the stability of these structures, podands have been identified as promising candidates for several different electrochemical applications. In this work, we use molecular dynamics simulations to investigate the solvation and selectivity of Na+, K+, and Li+ by different glycerol-derived solvents. The structural properties suggest that the solvent-cation association is stable over a very wide temperature range. A strong correlation is observed between the more electronegative oxygen sites and preferential interaction with the cations, which suggests that the electrostatic oxygen-ion interactions dominate the coordination between these species. Significantly more intense interactions are observed between the solvents and Li+, versus Na+ or K+. These molecular-level thermodynamic insights provide fundamental support for further exploring the performance of glycerol-derived podand complexes in Li+ capture applications and/or electrolyte formulations.