In this work, we proposed a chip on thermoelectric cooler (chip-on-TEC) for the active thermal management of high-power light-emitting diode (LED). The chip-on-TEC was prepared by electroplating a circuit layer on the cold-side substrate of thermoelectric cooling (TEC) and directly attaching LED chips on the circuit layer. Due to the Peltier effect of TE materials and the low thermal resistance of chip-on-TEC structure, the heat generated from the chips can be dissipated to the surrounding environment effectively. The performances of chip-on-TEC were studied by using the thermal simulation and packaging experiment. Compared with the traditional packaging structure, the working temperature of chip-on-TEC is greatly reduced under various chip currents. At the chip current of 1.0 A, the chip-on-TEC can reduce the working temperature from 232 °C to 114 °C (the reduction of 51%). Moreover, the light output power of LED is increased by 35.3%. The chip-on-TEC also can improve the light intensity and the light saturation point of LED. The results demonstrate that the chip-on-TEC is a promising thermal management for high-power LED packaging.