The temperature dependence of impact ionization coefficients of electrons and holes along 4H-SiC 〈0001〉 was determined in a wide temperature range from 156 K to 561 K. Photomultiplication measurements were conducted using several types of 4H-SiC photodiodes (PDs) with different structures under high vacuum conditions. The hole ionization coefficient showed a negative temperature dependence, which can be attributed to enhanced phonon scattering at elevated temperatures. Temperature dependence of the electron ionization coefficient was small, and this result may be ascribed to the simultaneous effects of enhanced phonon scattering and shrinkage of minigaps in the conduction band. Accuracy of the obtained results was verified by comparing the calculated breakdown voltage with the experimental breakdown voltage of various diodes.