A NMR investigation of 1,2,3,5,6,7-hexaoctyloxy-rufigallol (RufH8O) in the solid and columnar phases was performed. Four different isotopomers of RufH8O were synthesized and studied by various ¹³C NMR techniques. Deuterium-carbon dipolar interactions were measured and used for signal assignment, molecular structural analysis, and determination of orientational order. Experimental ¹³C chemical-shift tensors for the α methylene carbons were analyzed in terms of side chain conformation. Result showed that one of the aliphatic chains (R₃) adopts an in-plane structure, while the other two chains (R₁ and R₂) prefer out-of-plane conformations. Quantum-chemical calculations support the experimental findings.