In this paper, we report on a photoluminescence (PL) and EPR study of several semiinsulating (SI) 4H SiC samples showing the different compensation regimes due to the presence of V4+ and V3+of different concentration. The samples which contain only V3+ indicates the compensation regime NV≅ND-NA>0 with the Fermi level located in the upper half of the band gap. The presence of V4+ along with V3+ in the other two set of samples indicates the SI behavior of the samples with compensation regime NV>NA-ND>0. Considering that the samples revealed EPR spectrum of vanadium V3+, position of the Fermi level should be also in the upper half of the band gap and mixed conductivity could be expected. UD-3 PL spectrum was observed in vanadium doped SI 4H SiC presented in the samples in V3+/V4+ and V4+/V5+ charge states with compensation regime NV>NA-ND>0. The data obtained prove that the PL and EPR are suitable techniques in determination SI yield in SiC crystal.