The conformations of flexible chain molecules incorporated in a nematic environment have been investigated. The phase behaviours and orientational characteristics of 1,2-dimethoxyethane (DME) dissolved in 4′-methoxybenzylidene-4-n-butylaniline at low solute mol fraction have been reported in our previous paper. In this work, proton–proton and carbon–carbon dipolar coupling constant measurements were attempted in addition to2H NMR observations of quadrupolar splittings. These conformation-dependent properties were analysed according to the rotational isometric state (RIS) simulation scheme previously proposed. Our treatment rests on the assumption that the molecular axis of the chain should tend to align along the nematic field. Studies were further extended to a mixture of 1,2-diphenyloxyethane (DPE) with a nematic liquid crystal, 4,4′-azoxyanisole. Replacement of the terminal methyl groups in DME by phenyl groups leads to DPE. The results of the analysis indicate that the fraction of elongated conformers such asttttends to increase significantly on going from the isotropic to the liquid crystalline solution: DME; 9·4 to 15·6 per cent and DPE; 12·3 to 20·0 per cent. Thetgtform (tg+tortg−t) is the lowest-energy arrangement of these molecules. The fraction of this conformer also increases in DPE (26·8 to 40·0 per cent), while it decreases in DME (25·7 to 18·8 per cent). The conformational distributions of chain molecules were found to remain invariant over the range of concentration (0·5–6·0 mol per cent) and temperature (22·0–44·5°C) studied. It has been concluded that the observed variation of proton dipolar and deuterium quadrupolar couplings with concentration and temperature mainly arises from the orientational order of the molecular axis, which varies sensitively with the alignment of the surrounding solvent molecules. These results suggest that flexible chains are also participating in the nematic interaction by adjusting their configurations so as to enhance favourable interactions and suppress unfavourable steric repulsions when accommodated in an anisotropic potential field.