The intermolecular interactions between neighboring liquid-crystalline molecules, the esterification products of ethyl 4-[4'-oxy-4-biphenylcarbonyloxy]-4'-biphenylcarboxylate with poly(ethylene oxide)s (PEO) (DP = 12), were investigated using micro-Raman spectroscopy. To this end, the experiment was performed under the two different conditions, i.e., salt and temperature variations. We found that the modification of mesogenic Raman bands is mainly attributed to the changes in intermolecular interactions. The hydrogen bonding between the C=O functional group near the ethyl terminal and one of the hydrogen atoms in the PEO unit nearest the mesogenic moiety is responsible for the intermolecular interactions which affect the molecular packing. Van der Waals interaction is also taken into consideration in interpreting the experimental results. We suggest a mechanism for the conformational change during the solid-to-liquid crystal transition based on a systematic investigation of the related molecules.