We report an efficient one-step route to 2-fluoroalkylbenzimidazoles and-benzothiazoles via the condensation of fluorinated carboxylic acids and aromatic diamines or aminothiophenols. Additionally, we describe the syntheses of fluoroalkyl- azabenzimidazoles,-purines, and-imidazolopyrazines. This method is high-yielding with broad scope and is operationally simple with potential application to parallel synthesis.