The purpose of this study is to determine the vanadium defect levels in semi-insulating 4H-SiC and 6H-SiC using optical admittance spectroscopy (OAS). OAS data show several distinct peaks for the vanadium-doped SI 4H-SiC and 6H-SiC. Comparison of the data for the two polytypes suggests that peaks at 0.67 ± 0.02 eV and 0.70 ± 0.02 eV in 6H substrates and 0.75 ± 0.02 eV in 4H substrates are related to V3+/4+ levels at the cubic sites. A peak at 0.87 ± 0.02 eV in the 6H sample is assigned to the same defect level at the hexagonal site and the associated transition in 4H was observed at 0.94 ± 0.02 eV in our spectra. The donor levels are thought to be related to peaks at 1.94 ± 0.05 eV and 1.87 ± 0.05 eV in 4H and 6H samples, respectively. The differences between the values obtained from the optical admittance measurements and those reported in the literature are attributed to thermal relaxation and/or contributions from defect complexes.