We introduce a de Rham complex endowed with an integration map into the singular cochain complex which gives the de Rham theorem for every diffeological space. The theorem allows us to conclude that the Chen complex for a simply-connected manifold is quasi-isomorphic to the new de Rham complex of the free loop space of the manifold with an appropriate diffeology. This result is generalized from a diffeological point of view. In consequence, the de Rham complex behaves as a relevant codomain of Chen's iterated integrals. Furthermore, the precess of the generalization yields the Leray-Serre spectral sequence and the Eilenberg-Moore spectral sequence in the diffeological setting. The spectral sequences enable us to obtain computational examples of the new de Rham cohomology algebras for diffeological spaces containing the irrational torus and its related loop space.