Dendritic fibrous nanosilica (DFNS) was used as an efficient support to prepare a series of Al/DFNS/Pr-SO3H catalysts with different Si/Al molar ratios. The textural properties, morphology, structural feathers, acidity, and heterogeneous nature of the catalysts were characterized. The Al/DFNS/Pr-SO3H catalysts were utilized in the synthesis of n-hexyl levulinate (nHL) from alcoholysis of furfuryl alcohol with n-hexanol. Among these catalysts, 40Al/DFNS/Pr-SO3H, a Lewis and Bronsted bi-functional solid acid catalyst, showed the highest catalytic performance and the reaction conditions were optimized in the presence of this catalyst. Under optimum reaction conditions, n-hexyl levulinate yield and furfuryl alcohol conversion were 93.5% and 99.9%, respectively. Also, reusability experiments affirmed that 40Al/DFNS/Pr-SO3H catalyst can be recycled and reused for four times with an insignificant decrease in yield of product.