The bifunctional systems of the pyrene series, whose molecules contain pyrene nucleus and phenyl azide group, 1-[(4-azidobenzoyloxy)methyl]pyrene and 1-[(4-azidobenzoyl)amino]pyrene, were synthesized from pyrene for the first time. Original methods were developed to synthesize 1-nitropyrene and 1-aminopyrene, the key intermediates on the way to the target 1-[(4-azidobenzoyl)amino]pyrene.