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The main purpose of the authors is to investigate the structure properties of sets with finite perimeter. In order to do this, they give the notion of \\(G\\)-regular sets as level sets of functions regular with respect to the differentiable structure of \\(G\\). With a notion of intrinsic regular sets, it is possible to define \\(G\\)-rectifiability. Using this notion, the authors prove that the perimeter measure of a set \\(E\\) with finite \\(G\\)-perimeter is concentrated on a \\(G\\)-rectifiable set, the \\(G\\)-reduced boundary of \\(E\\). They prove also a representation formula for the perimeter measure and a divergence theorem, extending the classical De~Giorgi results in this framework. The proof relies on a blow-up technique on points of reduced boundary, showing that the blow-up converges to a subgroup. This phenomenon fails to happen in Carnot groups with step greater then 2, as shown by the Engel group. 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