By electron spin resonance (ESR) and photo-ESR, vanadium has been identified as an electrically amphoteric deep level impurity introducing both donor, D0/D+, and acceptor, A0/A-, states in the band gap of 4H- and 6H-SiC. The vanadium donor level in 6H-SiC has been located by photo-ESR near midgap, E(v) + 1.6 eV. Omnipresent titanium impurities were found to form complexes with nitrogen donors; the corresponding donor level of the (TiN) pair in 6H-SiC occurs at E(c) - 0.6 eV.