The expansion of the range of physico-chemical methods in the study of industrially significant α-olefin oligomers and polymers is of particular interest. In our article, we present a comparative Raman study of structurally uniform hydrogenated dimers, trimers, tetramers, and pentamers of 1-hexene and 1-octene, that are attractive as bases for freeze-resistant engine oils and lubricants. We found out that the joint monitoring of the disorder longitudinal acoustic mode (D-LAM) and symmetric C–C stretching modes allows the quantitative characterization of the number and length of alkyl chains (i.e., two structural characteristics), upon which the pour point and viscosity of the hydrocarbons depend, and to distinguish these compounds from both each other and linear alkanes. We demonstrated that the ratio of the contents of CH₂ and CH₃ groups in these hydrocarbons can be determined by using the intensities of the bands in the spectra, related to the asymmetric stretching vibrations of these groups. The density functional theory (DFT) calculations were applied to reveal the relations between the wavenumber and bandshape of the symmetric C–C stretching mode and a conformation arrangement of the 1-hexene and 1-octene dimers. We found that the branched double-chain conformation results in the splitting of the C–C mode into two components with the wavenumbers, which can be used as a measure of the length of branches. This conformation is preferable to the extended-chain conformation for hydrogenated 1-hexene and 1-octene dimers.