Effect of the pendant n-butyl group on shape recovery and tensile properties of polyurethane (PU) block copolymer was investigated. The grafted n-butyl group was intended to keep PU chains away and to deter molecular interaction between PU chains by its flexible chains, and thus improve shape recovery at subzero temperature while maintaining high and reproducible tensile properties and shape recovery at ambient temperature. The attachment of n-butyl group did not make any change in the molecular interaction and phase separation of hard and soft segments in PU structure as judged from IR and DSC analysis. Cross-link density and intrinsic viscosity increased with the increase of n-butyl content due to the partial cross-linking by the linking reagent. Shape recovery and shape retention were not diminished after cyclic shape memory tests. Finally, the effect of n-butyl group on low temperature shape recovery was compared with linear ones and the potential application of this finding was discussed.