The PVT and ²H-NMR characteristic of main-chain dimer liquid crystals having structures such as α,ω-bis[4,4'-cyanobiphenyl) oxy] alkane(CBA-10) were studied. In this work, V-T curves obtained from isobaris measurements on various pressures, volume changes were observed at the nematic-isotropic and nematic-crystal phase transition. The volume changes at the transition exhibit slight odd-even effect with respect to the number of methylene unit n. The values of the(ΔS_tr)_V obtained at the NI transition for CBA-10 was 12.6J/mol·K. The values of ( △S_CN)_V for the CN transition was estimated on the basis of DSC data : 65.3J/mol·K. For both transition, it was found that the correction about the volume change is significant, ranging from 40 to 60% of the total transition entropy observed under constant pressure. The RIS analysis of the spectra was performed so as to elucidate the conformational characteristics of the spacer in the nematic phase. The conformational entropy changes at both CN and NI interphases were estimated on the basis of the nematic conformations taken from the conformation map as well as those derived from the simulation. The estimated conformational entropy change values were then compared with the corresponding constant-volume entropies obtained from PVT measurements. The correspondence between both entropy values was found to be quite good in consideration of the uncertainties involved in both experiment and calculations.