Constant, real-time temperature monitoring of the supercapacitors for efficient energy usage is in high demand and seems to be crucial for further development of those elements. A fiber-optic sensor can be an effective optoelectronic device dedicated for in-situ temperature monitoring of supercapacitors. In this work, the application of the fiber-optic microstrucutre with thin zinc oxide (ZnO) coating fabricated in the atomic layer deposition process applied as a temperature sensor is reported. Such a structure was integrated with supercapacitors and used for the temperature measurements. Described sensors are built with the utility of the standard optical telecommunication fibers. The inner temperature of the supercapacitor was investigated in the range extending from 30 °C to 90 °C with a resolution equal to 5 °C. The sensitivity of temperature measurement is about 109.6 nW °C −1 . The fitting of the sensor was achieved with a correlation coefficient R 2 = 0.97.