Soft robotic systems are increasingly emerging as robust alternatives to conventional robotics. Here, we demonstrate the development of programmable soft actuators based on volume expansion/retraction accompanying liquid-vapor phase transition of a phase-change material confined within an elastomer matrix. The combination of a soft matrix (a silicone-based elastomer) and an embedded ethanol-impregnated polyacrylonitrile nanofiber (PAN NF) mat makes it possible to form a sealed compound device that can be operated by changing the actuator temperature above/below the boiling point of ethanol. The thermo-responsive actuators based on this principle demonstrate excellent bending ability at a sufficiently high temperature (>90 °C) - comparable with compressed air-based soft actuators. The actuator using the mechanism presented here is easy to manufacture and automate and is recyclable. Finally, the actuation mechanism can be incorporated into a wide variety of shapes and configurations, making it possible to obtain tunable and programmable soft robots that could have a wide variety of industrial applications.