Mesoporous bioactive glasses (MBGs) can be used as carriers for biomolecule delivery with improved functions. Although there are a great number of studies on drug delivery by MBGs, until now little work has been done to investigate the DNA gene transfection effect of MBGs. In this study, radial mesoporous bioactive glasses (rMBGs) were prepared by sol-gel process combined with a micro-emulsion method. The surface was further modified by amino groups in order to improve its affinity for DNA. Our study showed that rMBGs have good apatite-forming ability and cellular biocompatibility. In addition, rMBGs can enter cells in a time- and dose-dependent manner, and mainly localize in the cytoplasm. Agarose gel electrophoresis demonstrated that pOA-EGFP (containing the osteoactivin and the green fluorescent protein fusion gene) can be completely absorbed and protected from DNase I degradation by the aminated rMBGs. Additionally, the plasmid can be successfully expressed in cells transfected by rMBGs.