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The author investigates the real reductive linear Lie groups \\(G\\) that admit a left-invariant affine structure. The study of complete left-invariant affine structures leads to solvable groups. By a standard result, there is a one-to-one correspondence between such structures on \\(G\\) and LSA-structures on \\(\\mathfrak g\\), the Lie algebra of \\(G\\). Here, LSA stands for left-symmetric algebra. It is equivalent to study, then, the reductive Lie algebras \\({\\mathfrak g}={\\mathfrak z}\\oplus{\\mathfrak s}\\) where \\(\\mathfrak z\\) is the center of \\(\\mathfrak g\\) and \\(\\mathfrak s\\) is the semi-simple part, which will be assumed to be simple.   The first result is that the only such Lie algebras with one-dimensional center that admit LSA-structures are those whose simple part is (isomorphic to) \\({\\mathfrak g}{\\mathfrak l}(n)\\). (For algebras with a bigger center, there is a greater variety possible.) The second result of the paper is the description of LSA-structures on \\({\\mathfrak g}{\\mathfrak l}(n)\\) which are different from the standard one given by ordinary matrix multiplication. The others come as deformations of the matrix algebra. For \\(n>2\\), these (plus the standard one) exhaust the LSA-structures on \\(\\mathfrak g\\) and, hence, the left-invariant affine structures on 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