Semi‐insulating 6H–SiC crystals have been achieved by using controlled doping with deep‐level vanadium impurities. High resistivity undoped and semi‐insulating vanadium‐doped single‐crystals with diameters up to 50 mm were grown by physical vapor transport using an induction‐heated, cold‐wall system in which high purity graphite materials constituted the hot zone of the furnace. Undoped crystals werep‐type due to the presence of residual acceptor impurities, mainly boron, and exhibited resistivities ranging up to 3000 &OHgr; cm. The semi‐insulating behavior of the vanadium‐doped crystals is attributed to compensation of residual acceptors by the deep‐level vanadium V4+(3d1) donor located near the middle of the band gap. ©1995 American Institute of Physics.