<p>This work provides the thermophysical characterization of binary mixtures of 1-heptene and a homologous series of primary 1-alkanols (C₅–C₁₀) across the temperature range of 293.15 to 323.15&#xa0;K. The primary aim was to elucidate the intermolecular interaction mechanisms driving the non-ideal behavior of these systems. Experimental volumetric analysis revealed that excess molar volumes (<i>V</i>^<i>E</i>) exhibit consistent negative deviations across the entire composition range. Notably, the magnitude of these deviations displays a dual dependence: it increases with rising temperature and systematically intensifies as the alkyl chain of the alcohol extends. Concurrently, viscosity deviations (<i>Δη</i>) were found to be negative for all systems; however, their magnitude decreases as the hydrocarbon chain lengthens. This trend suggests that the incorporation of larger non-polar moieties in longer-chain alcohols attenuates the specific interaction effects observed in shorter homologs. To validate the volumetric trends, the Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) coupled with Density Gradient Theory (DGT) was utilized for excess molar volume modeling. The theoretical predictions demonstrated remarkable agreement with experimental data across all studied systems, yielding Average Absolute Relative Deviations (AARD) ranging from 1.4 to 2.4% and <i>R</i>^<i>2</i> values of 0.998 or higher. This confirms the robustness of the combined DGT + PC-SAFT framework in accurately describing the thermodynamic behavior of these olefin-alcohol blends.</p>