Gene delivery biomaterials need to be designed to efficiently achieve nuclear delivery of plasmid DNA. To achieve this goal, various extracellular and intracellular barriers must be overcome. Polycationic polymers have been used to package DNA and other nucleic acids within sub-micron sized particles, offering protection from shear-induced or enzymatic degradation. However, cytotoxicity issues coupled with limited transfection efficiencies minimize the effectiveness of this approach. In an effort to improve upon existing technologies aimed at delivering nucleic acids, we have explored an alternative approach to DNA packaging. Our method involves the utilization of peptide nucleic acids (PNAs) to directly functionalize DNA and allow for the formulation of modified plasmids complexed with lower molecular weight polymers. PNAs are nucleic acid analogs with a peptide backbone that can bind to double stranded DNA to form a stable PNA-DNA-PNA triplex. Polyethylene glycol (PEG) chains can be directly added to a plasmid via this conjugation chemistry, providing a steric layer which prevents opsonization and promotes the colloidal stability of the DNA prior to its complexation with polycations. Peptides with specific amino acid sequences related to physiological targets can also be incorporated onto this hierarchically designed structure, promoting preferential delivery to a particular location. We have created DNA-PNA-peptide conjugates using this approach and have post-complexed the DNA using spermidine and polyethylenimine. We have characterized the size, morphology, and surface chemistry of these conjugates by dynamic light scattering, atomic force microscopy, and zeta potential analyses, respectively. We can create 100 – 300 nm stabilized particles whose diameter depends upon the nature and concentration of the condensing polycations. Proof of principle of our PNA-based design will lay the foundation for their use as tools to probe the kinetics of intracellular transport.