Three pure jojoba wax-like esters (JLEs), i.e., octadec-9-enyl dec-9-enoate (JLE 28(1)), dec-9-enyl oleate (JLE 28(2)), and dec-9-enyl dec-9-enoate (JLE-20), were synthesized from fatty acids and fatty alcohols. Calorimetric, solid fat content evolution, and flow data were used to elucidate the phase behavior of the JLEs. It was clearly established that the length of the terminal alkyl chain and orientation of the linking group in the side chains of the bent-core molecules play an important role in the phase development of the JLEs and ultimately their physical properties. Measurable differences in all physical properties investigated were detected between the isomers based on the position of the ester group in the molecule, leading to informed choices on what isomer should be synthesized for similar monoesters for specific applications.