N , O -Diarylhydroxylamines generally favor the [3,3] sigmatropic shift rearrangement. Possible N/O[1,3] sigmatropic shift rearrangements of multisubstituted N , O -diarylhydroxylamines were investigated experimentally with rationally designed substrates, which were generally in situ prepared from suitable nitroaryl halides and N -arylhydroxylamines via aromatic nucleophilic substitution. The results indicate that both N - and O -(2,4,6-trimethylphenyl)hydroxylamines still favor the [3,3] sigmatropic shift followed by tautomerization rather than N[1,3] and O[1,3] sigmatropic shifts and the rearranged products of N -(2,4,6-trimethylphenyl)hydroxylamines further undergo an intramolecular nucleophilic addition to afford dibenzo[ b , d ]furan-4a(9b H )-amine derivatives, while N -(4-mono- and 3,5-disubstituted phenyl)- O -(2,4,6-trinitrophenyl)hydroxylamines favorably first undergo the O[1,3] sigmatropic shift followed by tandem Smiles rearrangement and amide/ester exchange reactions, generating 2-arylaminoaryl benzoate derivatives. N -Phenyl- O -(2,4,6-trinitrophenyl)hydroxylamines undergo tandem double O[1,3] sigmatropic shift rearrangement to produce formal O[1,5] shift products. However, O -(2,6-dinitrophenyl)- N -(4-substituted phenyl)hydroxylamines undergo tandem O[1,3] and double [3,3] sigmatropic shift rearrangements to give formal 3,5-shift products. The proposed mechanism is rationalized by density functional theory (DFT) calculations. The current investigation provides not only a comprehensive understanding of the chemoselective sigmatropic shift rearrangements of N , O -diarylhydroxylamines, but also some novel synthetic strategies for dibenzo[ b , d ]furanamines, diarylamines, diaryl ethers, 2'-amino-[1,1'-biphenyl]-2(1 H )-one, and 2'-amino-[1,1'-biaryl]-4-ol derivatives.