Nitrosoarenes typically participate in a monomer–dimer equilibrium.  The azobenzene N,N-dioxide (Ar(O)N=N(O)Ar) dimers, which are often pale yellow, are generally favored in the solid state, whereas the deep-green monomers are favored in dilute solution or at higher temperatures.  They exist as cis and trans' isomers.
When stored in protic media, primary and secondary nitrosoalkanes isomerize to oximes.  
Due to the stability of the nitric oxide free radical, nitroso organyls tend to have very low C–N bond dissociation energies: nitrosoalkanes have BDEs on the order of , while nitrosoarenes have BDEs on the order of .  As a consequence, they are generally heat- and light-sensitive.  Compounds containing O–(NO) or N–(NO) bonds generally have even lower bond dissociation energies.  For instance, N-nitrosodiphenylamine, PhN–N=O, has a N–N bond dissociation energy of only . Organonitroso compounds serve as a ligands giving transition metal nitroso complexes.