Amidyl radicals possessing Δ4,5, Δ5,6, and Δ6,7 double bonds were generated from the photodecomposition of nitrosamides and chloramides and the products were identified. Dichotomies of amidyl radical reactivities were discovered and compared with published kinetic rate constants. In complete reversal to intermolecular reactivities, intramolecularly the alkenyl amidyl radicals preferentially add to the double bonds rather than abstract a C-5 hydrogen even if it is allylic. In intramolecular competition, amidyl radicals add to an acyl side chain double bond more efficiently than to an alkyl one; this is just the opposite to intramolecular H-abstraction of amidyl radicals. Taken together with the published results, it is established that, in intramolecular attacks of double bonds, amidyl radicals selectively undergo the propia-addition to generate an exo-cyclic radical rather than the longa-addition to an endo-cyclic radical: this rule should replace the old one that amidyl radicals preferentially cyclize to form five-membered rings if choices are available.