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The de Rham theorem is proved in this setting.  The \\textit{de Rham complex} \\(\\Omega^\\ast(X)\\) for a diffeological space \\(X\\) was introduced by [\\textit{J. M. Souriau}, Lect. Notes Math. 836, 91--128 (1980; Zbl 0501.58010)], see also [\\textit{P. Iglesias-Zemmour}, Diffeology. Providence, RI: American Mathematical Society (AMS) (2013; Zbl 1269.53003)].  The author considers another \\textit{singular de Rham complex} \\(A^\\ast_{DR}(S^D_\\bullet(X))\\), also denoted by \\(A^\\ast(X)\\), that can be regarded as a diffeological variant of Sullivan's polynomial simplicial forms for a topological space [\\textit{D. Sullivan}, Publ. Math., Inst. Hautes \u00c9tud. Sci. 47, 269--331 (1977; Zbl 0374.57002)].  Finally, there is the cochain complex \\(C^\\ast(X)=C^\\ast(S^D_\\bullet(X)_{\\mathrm{sub}})\\) defined by \\textit{G. Hector} [in: Analysis and geometry in foliated manifolds. Proceedings of the VII international colloquium on differential geometry, Santiago de Compostela, Spain, July 26--30, 1994. Singapore: World Scientific. 55--80 (1995; Zbl 0993.58500)] of the \\textit{smooth singular simplicial set} \\(S^D_\\bullet(X)_{\\mathrm{sub}}\\) of \\(C^\\infty\\)-maps from \\(\\Delta^n_{\\mathrm{sub}}\\) into \\(X\\), where \\(\\Delta^n_{\\mathrm{sub}}\\) is the diffeological space whose underlying set is the standard \\(n\\)-simplex, equipped with the sub-diffeology of the affine space.  The main result (Theorem 2.4) is that an appropriate \\textit{integration map} between \\(A^\\ast(X)\\) and \\(C^\\ast(X)\\) induces an isomorphism of algebras in cohomology, for every diffeological space \\(X\\).  The relationship between the cochain algebras \\(\\Omega^\\ast(X)\\) and \\(A^\\ast(X)\\) is given by a so-called \\textit{factor map}, which is proved to be a quasi-isomorphism if \\(X\\) is a finite dimensional smooth CW-complex. Moreover, there is a cochain homotopy equivalence between \\(C^\\ast(X)\\) and \\(C^\\ast_{\\mathrm{cube}}(X)\\), the normalized cubic cochain complex whose \\(p\\)-simplices are smooth maps from \\(\\mathbb{R}^p\\) to \\(X\\).  Another suitable choice of simplicial sets enables the author to construct the Leray-Serre spectral sequence and the Eilenberg-Moore spectral sequence for fibrations in the category of diffeological 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