This communication presents the pH-dependent chelation of Zn2+ ions with the imidazolegroups of poly(1-vinylimidazole) (PVIm) and DNA polyion complex formation with the zinc-chelated PVIm (PVIm-Zn) via chelated Zn2+ ions. The resulting PVIm-Zn/DNA complexes exhibit no significant cytotoxicity and show outstanding gene expression.