Although charge-transfer compounds based on tetrathiafulvalene (TTF) derivatives have been intensively studied, {[cation](n+)center dot[TTFs](n-)} ion pair charge-transfer (IPCT) salts have not been reported. The aim of this research is to introduce functional organic cations, such as photoactive methyl viologen (MV2+), into the negatively charged TTF-metal coordination framework to obtain this new type of IPCT complex. X-ray structural analysis of the four compounds (MV)(2)[Li-4(L)(2)(H2O)(6)] (1), {(MV)(L)[Na-2(H2O)(8)]center dot 4H(2)O}(n) (2), {(MV)[Mn(L)(H2O)(2)]center dot 2H(2)O}(n) (3), and [(MV)[Mn(L)(H2O)(2)]}(n) (4), reveals that the electron donor (D) TTF moiety and the electron acceptor (A) MV2+ form a regular mixed-stack arrangement in alternating DADA fashion. The TTF moiety and the MV2+ cation are essentially parallel stacked to form the column structures. The strong electrostatic interaction is a main force to shorten the distance between the cation and anion planes. Optical diffuse-reflection spectra indicate that charge transfer occurs in these complexes. The ESR and magnetic measurements confirm that there is strong charge-transfer-induced partial electron transfer. Compounds 2, 3, and 4 show an effective and repeatable photocurrent response. The current intensities of 3 and 4 are higher than that of 2, which reflects that the coordination center of the Mn(H) ion has a great effect on the increasing photocurrent response.