The neutrino mass experiment KATRIN requires a stability of 3 ppm for the retarding potential at - 18.6 kV of the main spectrometer. To monitor the stability, two custom-made ultra-precise high-voltage dividers were developed and built in cooperation with the German national metrology institute Physikalisch-Technische Bundesanstalt (PTB). Until now, regular absolute calibration of the voltage dividers required bringing the equipment to the specialised metrology laboratory. Here we present a new method based on measuring the energy difference of two Kr-83m conversion electron lines with the KATRIN setup, which was demonstrated during KATRIN's commissioning measurements in July 2017. The measured scale factor M = 1972.449(10) of the high-voltage divider K35 is in agreement with the last PTB calibration 4 years ago. This result demonstrates the utility of the calibration method, as well as the long-term stability of the voltage divider.