Photoinduced transient spectroscopy (PITS) has been applied to study electronic properties of point defects associated with charge compensation in semi-insulating (SI) 6H-SiC substrates. The photocurrent relaxation waveforms were digitally recorded in a wide temperature range of 20–800 K and in order to extract the parameters of defect centres, a two-dimensional analysis of the waveforms as a function of time and temperature has been implemented. As a result, the processes of thermal emission of charge carriers from defect centres were seen on the spectral surface as the folds, whose ridgelines depicted the temperature dependences of emission rate for detected defect centres. The new approach was used to compare the defect levels in vanadium-doped and vanadium-free (undoped) SI 6H-SiC wafers.