In this study, we explore the spectral properties of the distribution matrices of the mapping method and its relation to the distributive mixing of passive scalars. The spectral (or eigenvector-eigenvalue) decomposition of these matrices constitutes discrete approximations to the eigenmodes of the continuous advection operator in periodic flows. The eigenvalue spectrum always lies within the unit circle and due to mass conservation, always accommodates an eigenvalue equal to one with trivial (uniform) eigenvector. The asymptotic state of a fully chaotic mixing flow is dominated by the eigenmode corresponding with the eigenvalue closest to the unit circle (“dominant eigenmode”). This eigenvalue determines the decay rate; its eigenvector determines the asymptotic mixing pattern. The closer this eigenvalue value is to the origin, the faster is the homogenization by the chaotic mixing. Hence, its magnitude can be used as a quantitative mixing measure for comparison of different mixing protocols. In nonchaotic cases, the presence of islands results in eigenvalues on the unit circle and associated eigenvectors demarcating the location of these islands. Eigenvalues on the unit circle thus are qualitative indicators of inefficient mixing; the properties of its eigenvectors enable isolation of the nonmixing zones. Thus important fundamental aspects of mixing processes can be inferred from the eigenmode analysis of the mapping matrix. This is elaborated in the present paper and demonstrated by way of two different prototypical mixing flows: the time-periodic sine flow and the spatially periodic partitioned-pipe mixer.