Controlling liquid–solid triboelectrification is highly demanded in a wide range of applications, from electrostatic prevention to energy collection and utilization. Except for traditional unidirectional and irreversible ways, smart approaches are required urgently. Here, a novel temperature response liquid–solid triboelectric nanogenerator (TENG) is reported on the basis of a polycaprolactone (PCL) covered fluorinated alumina for tunable triboelectrification. The PCL conformation is regulated by temperature to endow the substrate controllable surface component and interfacial wettability to manipulate the liquid–solid triboelectricity flexibly. As the temperature rises from 20 to 40 °C, the short circuit current and the open‐circuit voltage of the PCL‐based TENG are reduced by more than 40 times. When the temperature drops to 20 °C, the electrical output can return to its original level again. Moreover, after one month, the electrical signal is still reversible and stable. In addition to water, the electrical output of organic liquid, such as ethylene glycol, also responds well to temperature. This work initially provides a new strategy for achieving the customizable manipulation of liquid–solid triboelectrification by polymer surface reorganization, gives a new idea for in situ monitoring the interfacial wettability changes, and configures the reconstruction of amphiphilic polymer using triboelectricity.