4-Substituted phenyl 4'-substituted biphenyl-4-carboxylates with methyl and/or methoxy groups have been synthesized and proved to be enantiotropic nematogens. Crystal structures have been determined for 4-methylphenyl 4'-methylbiphenyl-4-calboxylate (1-1), 4-octylphenyl 4'-methoxybiphenyl-4-calboxylate (10-8), and 4-octylphenyl 4'-methylbiphenyl-4-calboxylate (1-8). 10-8 has a packing mode with one-dimensional chains of close arrangements of ester linkages, as previously found for many biphenyl esters with at least one alkoxy chain. 1-8 and 1-1 have a similar packing of core moieties with ester linkages far from each other, but different from 8-8 and 8-1 (4-octylphenyl and 4-methylphenyl 4-octylbiphenyl-4'-carboxylates), suggesting the dominant role of a chain attached to a biphenyl moiety in intermolecular interactions.