The structure determination of intrinsic defects in 4H-SiC, 6H-SiC, and 3C-SiC by means of EPR is based on measuring the angular dependence of the 29Si/13C hyperfine (HF) satellite lines, from which spin densities, sp-hybrid ratio, and p-orbital direction can be determined over major atoms comprising a defect. In most cases, not only the assignment of the variety due to the inequivalent sites (h- and k-sites in 4H-SiC) but also the identification of the defect species is accomplished through the comparison of the obtained HF parameters with those obtained from first principles calculations. Our works of identifying vacancy-related defects such as the monovacancies, divacancies, and antisite-vacancy pairs in 4H-SiC are reviewed. In addition, it is demonstrated that the observation of the central line of the TV2a center of S = 3/2 has been achieved by pulsed-ELDOR. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.