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In this paper, we determine the structure of the Witt group W(X) of X in terms of certain birational invariants of X and compute W(X) explicitly for a projective, real, rational surface X (i.e. X with \\(X_{{\\mathbb{C}}}=X\\times_{Spec({\\mathbb{R}})}Spec({\\mathbb{C}})\\) birational to \\({\\mathbb{P}}^ 2({\\mathbb{C}}))\\). More precisely, if X is a projective, real, rational surface such that the space X(\\({\\mathbb{R}})\\) of \\({\\mathbb{R}}\\)-rational points of X is non-empty, we prove that \\(W(X)\\simeq {\\mathbb{Z}}^ s\\oplus ({\\mathbb{Z}}/2)^{s-1}\\), where s is the number of real connected components of X(\\({\\mathbb{R}})\\), which is known to be finite and a birational invariant. The proof uses a result of J.-L. Colliot-Th\u00e9l\u00e8ne and R. Parimala relating real components of algebraic varieties to unramified cohomology. If, on the other hand, \\(X({\\mathbb{R}})=\\emptyset\\), we prove that W(X)\\(\\simeq {\\mathbb{Z}}/2\\oplus {\\mathbb{Z}}/4\\). The proof of this uses a result of R. Parimala and the author, that for such an X, the level of the function field \\({\\mathbb{R}}(X)\\) is 2. These results along with a theorem of Silhol, imply that a smooth, real, rational surface is birational to \\({\\mathbb{P}}^ 2({\\mathbb{R}})\\) if and only if W(X)\\(\\simeq 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