Unlike the photographically important silver halides, large NaCl single crystals can be grown from solution. In such NaCl crystals, with doping comparable to practical AgCl and AgBr microcrystals, three stable Rh centers were detected and studied by electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR). The primary center was identified as a nonlocally compensated[RhCl6]4−complex, at variance with earlier reported EPR work. By lack of sufficient EPR and/or ENDOR evidence, the identity of the two other Rh related centers with orthorhombic and isotropic symmetry respectively, remains rather speculative. ©1997 American Institute of Physics.