Diesel fuel combustion generates soot particles, which are harmful for human health and the environment. To reduce soot emission, various solutions are proposed in the literature such as the use of metal-additives in fuels, fuel blending with biofuels, and the use of diesel particulate filters. This study analyses the effect of the addition of a bicyclic monoterpene hydrocarbon biofuel, α-pinene to diesel in different proportions on the fuel cetane number, sooting propensity, and the physicochemical properties of soot nanoparticles. The addition of 10% α-pinene to diesel exhibited a synergistic effect on sooting tendency and reduced the threshold sooting index of diesel by 21%, even though α-pinene is an unsaturated hydrocarbon, and had a minimal impact on cetane number, which reduced from 63.5 for diesel to 61.5 for the blended fuel. The influence of α-pinene addition to diesel on soot nanostructural characteristics and reactivity is determined through different characterization approaches including HRTEM, TGA, XRD, SEM-EDX, and EELS. The results indicate that α-pinene addition to diesel imposes curvatures in soot nanostructure, creates relatively smaller fringes (PAHs) in soot, and reduces soot aromatic content to improve soot oxidation rate.