A novel and efficient copper-catalyzed strategy for the synthesis of diverse pyridines through the [3+3] annulation of ketones with oxime acetates has been reported. It is very convenient to obtain various unsymmetrical 2,6-diarylpyridines by changing different substrates. The rare copper-catalyzed direct difunctionalization of saturated ketones for the synthesis of nitrogen heterocycles is developed. This protocol has excellent functional group tolerance, readily available raw materials, high chemoselectivity and broad substrate scope.