In this study, novel alpha-truxillic and beta-truxinic acid-based, bio-derived diesters have been developed as internal donors for preparing Ziegler-Natta (ZN) catalysts. Impacts of these bio-derived diesters were investigated on the chemical composition, the morphology, the mode of adsorption, and the propylene polymerization performance of the catalysts in comparison to the most widely used fourth-generation catalyst containing dibutyl phthalate. The molecular structures of the diesters and the particle morphology of the catalysts were preserved in the catalyst preparation. The bio-derived diesters afforded ZN catalysts with a reasonable activity and stereo specificity in propylene polymerization along with similarly broad molecular weight distribution (MWD) as the phthalate-based catalyst. Another promising feature of the catalysts was an opposite hydrogen response in terms of expansion of MWD upon the addition of H-2.