The photochemistry of some 3-N-alkylamino-5-perfluoroalkyl-1,2,4-oxadiazoles in the presence of nitrogen nucleophiles such as ammonia and primary and secondary aliphatic amines has been investigated. The primary photolytic intermediate from the cleavage of the ring O-N bond follows two distinct and competing pathways leading to (i). 5-perfluoroalkyl-1,3,4-oxadiazoles, through the ring contraction-ring expansion photoisomerization route favored by the presence of the base or (ii). 5-perfluoroalkyl-1,2,4-triazoles, through the intervention, as an internal nucleophile, of the exocyclic N-alkylamino moiety of the oxadiazole followed by the attack of the external nitrogen nucleophile and subsequent heterocyclization. Some comments on the photoreactivity of fluorinated oxadiazoles and on the applications of these photoprocesses in the synthesis of target fluorinated structures are emphasized. In this context, irradiations of 3-perfluoroalkanoylamino-4-phenylfurazan in the presence of primary aliphatic amines are reconsidered as feasible one-pot synthetic methodologies toward fluorinated heterocycles. X-ray analysis of two representative products 1-methyl-3-methylamino-5-perfluoroheptyl-1,2,4-triazole and 2-methylamino-5-trifluoromethyl-1,3,4-oxadiazole confirmed the proposed structures and furnished interesting information on the crystal packing of these fluorinated five-membered heterocycles.