We report here that the Re/SiO2 catalyst can be a suitable low-cost catalyst for processing polyols into acetals in solvent-free conditions with a high conversion rate and selectivity up to 100% in mild conditions. During a complex investigation, we broadly tested the blending potential of the acetals that were formed by measuring properties such as density, viscosity, isentropic compressibility, isobaric thermal expansion, cetane number and other parameters of both the crude additives and the blends that were prepared with petroleum diesel oil. The results indicate that the investigated acetals can generally be used for blending with petroleum diesel oil in order to obtain the valuable biofuels that are in great demand in the contemporary transportation industry due to the regulatory restrictions that have been introduced in order to protect the environment.