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The structures of two polymorphs of [MnTClPP][TCNE] have been determined by Rietveld refinement of the X-ray powder diffraction method. Samples were prepared by thermolysis of the toluene and CH2Cl2solvates, [MnTClPP][TCNE]·2Sol (Sol = PhMe, CH2Cl2). The desolvated structures are similar to their solvates, consisting of alternating stacks of the molecular donor and acceptor. Among the four structures, the largest changes are observed for the dihedral angle between the mean Mn(N4)TPPand [TCNE]•−planes, and the Mn−(N−C)TCNEangle. A magnetostructural correlation between the intrachain coupling and both the dihedral angle between the mean Mn(N4)TPPand [TCNE]•−planes and Mn−(N−C)TCNEangles is observed. This is in accord with the intrachain coupling arising from the overlap of MnIIIdz2-like singly occupied molecular orbital (SOMO) and the zcomponent of the [TCNE]•−π* (πz*) SOMO, which increases with decreasing dihedral angle between the mean Mn(N4)TPPand [TCNE]•−planes and Mn−(N−C)TCNEangle.