Electron-transfer-facilitated dissolution, ion insertion, and desorption associated with an MMX-type quasi-one-dimensional iodide-bridged dinuclear Pt complex (MMX chain) have been investigated for the first time. K2(NC3N)[Pt2(pop)4I]·4H2O (1) (NC3N(2+) = (H3NC3H6NH3)(2+); pop = P2H2O5(2-)) is a semiconductor with a three-dimensional coordination-bond and hydrogen-bond network included in the chain. The cyclic voltammetry of 1 was studied by using 1-modified electrodes in contact with acetonitrile solutions containing electrolyte. The chemical reversibility for oxidation of 1 depended on the electrolyte cation size, with large cations such as tetrabutylammonium (Bu4N(+)) being too large to penetrate the pores formed by the loss of K(+) and NC3N(2+) upon oxidation. The potential for reduction of 1 decreased as the cation size increased. The presence of the acid induced additional well-defined processes but with gradual solid dissolution, attributed to the breaking of the coordination-bond networks.