Polyethylenimines exhibit unique intrinsic properties, which make them potential gene delivery agents. However, nonspecific interactions and cytotoxicity in the cells/tissues have significantly hampered their use in clinical applications. To subside these concerns, plant-based cyclitols, shikimic and quinic acids, have been tethered to polyethylenimine (PEI) to fabricate shikimoyl-PEI (SP) and quinoyl-PEI (QP) conjugates under mild coupling conditions. On interactions with plasmid DNA, the size and zeta potential of SP and QP complexes were found in the range of ∼245–158 nm and ∼ +22–10 mV, respectively. Subsequent assessment of these complexes revealed that cytocompatibility (∼90%–94%) and transfection efficiency (∼90% cells transfected) were significantly higher as compared to the native PEI/pDNA and Lipofectamine/pDNA complexes. Further, a higher degree of pDNA release was also obtained from SP/DNA and QP/DNA complexes. A decrease in GFP expression was observed in a competitive assay on RAW 264.7 cells, which reflected receptor-mediated internalization of SP and QP/DNA complexes. Besides, both SP and QP conjugates also displayed efficient antimicrobial activity against differential pathogenic strains of bacteria. Of these conjugates, QP conjugates exhibited promising anticancer activity against variable cell lines such as RAW 264.7, MCF-7, HepG2 cells. Altogether, these results advocate the promising potential of SP and QP conjugates as efficient gene delivery agents having effective antimicrobial and anticancer competence.