The biocleavable star-shaped vectors (CD-SS-PGEAs) consisting of nonionic β-cyclodextrin (β-CD) cores and disulfide-linked low-molecular-weight poly(glycidyl methacrylate) (PGMA) derivative arms with plentiful flanking secondary amine and hydroxyl groups were successfully proposed for highly efficient gene delivery. A simple two-step method was first adopted to introduce reduction-sensitive disulfide-linked initiation sites of atom transfer radical polymerization (ATRP) onto β-CD cores. The disulfide-linked PGMA arms prepared subsequently via ATRP were functionalized via the ring-opening reaction with ethanolamine (EA) to produce the cationic EA-functionalized PGMA (PGEA) arms with plentiful secondary amine and nonionic hydroxyl units. The cationic PGEA arms can be readily cleavable from the β-CD cores under reducible conditions. Such biocleavable star-shaped CD-SS-PGEA vectors possessed the good pDNA condensation ability, low cytotoxicity, and efficient gene delivery ability.