Various polysulfone (PSf)-based shape memory polymers (SMPs) with tunable transition temperature (T-trans) are prepared via atom transfer radical polymerization. Hard segments of SMPs are formed by PSf backbone which are then combined with nonlinear derivatives of poly(ethylene glycol) (PEG), that is, poly(ethylene glycol)methyl ether methacrylate as the soft segment. The melting temperature (T-m) of soft segments is shown to be an effective stimulus to achieve shape memory behavior. T-m values of graft copolymers are found in the range of body temperature from 32.7 to 39.1 degrees C, and SMPs are obtained with a maximum strain around 464%, tensile strength up to 6.8MPa, and shape recovery ratio up to 99%. It is shown that the characteristic of SMPs can be tuned by altering the topology and the ratio of soft/hard segments. PSf-based SMPs can be suitable for various applications since the material's properties can be tailored for specific applications.