Copper-catalyzed amination of aryl boronic acids with alkylnitrites leading to symmetrical diarylamines with a practical 50-80% yield was elaborated. Two C(sp2)-N bonds are formed in the one-pot process under mild conditions. This new approach to diarylamines is a complement to the Cu-assisted reductive amination of aryl boronic acids avoiding preliminary synthesis of nitrosoarenes. The possible reaction scheme based on quantum chemical calculations was suggested, clarifying key intermediates.