Summary: The synthesis of azoalkanes such as azocyclohexane ( 1 ) and 4,4′‐bis(cyclohexylazocyclohexyl)methane ( 2 ) and their use as flame retardants in polymeric substrates is reported. For the first time it is demonstrated that azoalkanes alone can effectively provide flame retardancy and self‐extinguishing properties to poly(propylene) films at a very low concentration of 0.25 to 0.5 wt.‐%. All the poly(propylene) formulations passed DIN 4102‐1/B2 standards and the instant azoalkane‐containing poly(propylene) blends show no discoloration.