Neutral N-pyrazolyl radicals [3,5-R(2)pz](center dot) as reactive intermediates were generated by one-electron oxidization of the corresponding 3,5-disubstituted pyrazolato anions [3,5-R(2)pz](-) (R = tBu, Ph) with BiCl3 and trapped by the use of 5,5-dimethyl-1-pyrroline-N-oxide as a spin trap, which was confirmed by electron paramagnetic resonance spectral analysis. With dimerization of the postulated pyrazolato low-valent Bill radical species, two novel paddlewheel pyrazolatodibismuthanes [L-2(Bi-Bi)L-2] [L = eta(1),eta(1)-3,5-R(2)pz; R = tBu (5 alpha, 5 beta, and 5 gamma), Ph (6)] were isolated and structurally characterized.