Preparation of nanoscale Janus particles that can respond to external stimulation and, at the same time, be prepared using an easily achievable method presents a significant challenge. Here, we have demonstrated the shape memory of Janus nanoparticles (SMJNPs) with a multifunctional combination of Janus nanostructure and a shape memory effect, composed of a well-defined amphipathic sucrose-poly(ε-caprolactone) cross-linked network. A sudden negative pressure method was first used to prepare the Janus-shaped nanoparticles (temporary shape), which can switch their shape and wettability. The Janus-shaped nanoparticle is an amphipathic structure composed of hydrophilic and hydrophobic parts. Moreover, in response to temperature, the nanoparticle can recover their nanosphere state via a shape memory process. The novel Janus nanoparticles with the shape memory property also show a great potential for application such as drug delivery.