Novel reactivity for π-conjugated triazenes is herein reported. This observed and unprecedented triazene reactivity gave access to oxidation and substitution reactions. These transformations include successful synthesis of aldehydes, ketones, ethers, and sulfides from readily available organic azides via π-conjugated triazene intermediates. Notably, the afforded adducts were obtained in good yields, at room temperature, and in the absence of added metal catalysts.