Multicomponent phase change microfibers, which can storage and release thermal energy in a stepwise manner, are firstly prepared through a facile one-step multifluidic compound-jet electrospinning with temperature control. The multiresponsive effect benefits from a special multichannel tubular microstructure that could controllably encapsulate different phase change materials into the channels independently. Aside from the fabrication of multicomponent phase change microfibers, the melt multifluidic compound-jet electrospinning is promising for applications related to microencapsulation and multifunctional material fields.