Phase change materials (PCMs) offer a promising technology for thermal energy storage, load leveling, and peak shifting applications. A desirable PCM has a melting temperature within the temperature boundaries of its application and a high change in enthalpy on melting. Knowledge of the relationships between these thermodynamic properties and molecular structure would advance informed selection of PCM candidates for a given application. In the present investigation, the relationship between structure (length of alkyl chains) and melting properties has been investigated for isomeric esters, showing that esters containing longer individual alkyl chains have higher melting temperatures and higher enthalpy changes on melting. The melting entropy changes, however, are relatively independent of the alkyl chain distribution.