Phenylboronic acid (PBA) possesses good affinities to glycoproteins on cell surfaces, as well as stable fluorescence properties. Recently, it was found that ethanolamine (EA)-decorated poly(glycidyl methacrylate) (PGMA), namely PGEA, exhibited promising applications as effective gene vectors. In this work, a strategy to prepare series of starlike PGEA vectors (s-PGEA-B) with flanking PBA groups was proposed for the development of high-efficient multifunctional gene delivery systems. Compared with the s-PGEA vectors without PBA groups, the corresponding s-PGEA-B counterparts showed the greater ability to bind pDNA. The sizes of the formed s-PGEA-B/pDNA nanoparticles were ~100 nm at higher N/P ratios. The s-PGEA-B/pDNA complexes exhibited enhanced cellular internalization and transfection efficiencies, particularly in the cell lines with abundant cell surface glycoproteins. The cellular internalization mediated by s-PGEA-B with 30% of PBA content was about 85%, much higher than that (about 53%) of the corresponding s-PGEA in HepG2 cells. In addition, the simultaneous fluorescence emitted from s-PGEA-B provided convenient observation for locating gene vectors during the transfection processes. This present work would provide new useful information for the design of multifunctional gene delivery systems. 16increasing amounts of polycations helped to condense pDNA at moderate N/P ratios, while at higher N/P ratios the excess polycations did not participate in complexing.Compared with s-PGEA, the corresponding s-PGEA-B exhibited stronger ability to compress pDNA into smaller nanoparticles particularly at the low N/P ratios, further confirming that the introduction of PBA groups contributed to condense pDNA. Fig. 3(b) shows the corresponding zeta potentials of the complexes at the N/P ratios from 5 to 35. At the low N/P ratio of 5, the ζ-potentials of s-PGEA-B/pDNA complexes were slightly higher than those of the corresponding s-PGEA/pDNA complexes, probably due to the stronger condensation ability of s-PGEA-B. However, at the higher N/P ratios, particularly N/P ratio of 30, s-PGEA-B/pDNA complexes exhibited the moderately lower ζ-potentials than the corresponding s-PGEA/pDNA complexes. As mentioned above, at higher N/P ratios the excess s-PGEA-B and s-PGEA polycations did not participate in complexing. The amount increase of weakly negative-charged PBA groups may fairly decrease the ζ-potentials of complex surfaces. The still positive ζ-potentials would make the s-PGEA-B/pDNA complexes possess good affinity to the negative-charged cell membranes. The visualized morphologies of complexes were presented in Fig. 4. The representative AFM images of s-PGEA1/pDNA and s-PGEA1-B2/pDNA complexes revealed that the polycations condensed pDNA into uniform nanospheres with the diameter of around 100 nm.