The interaction of manganese(ii) phthalocyanine with 7,7,8,8-tetracyanoquinodimethane and its perfluoro derivative proceeds with the oxidation of Mn and the reduction of the acceptor molecules to give the first mixed single crystals of manganese(iii) phthalocyanine with TCNQ/F₄-TCNQ radical anions. The crystals have unusual structures with C-H⋯π interactions between the ions and their orthogonal arrangement, as well as remarkable redox properties. The charge transfer was proved by spectroscopic and magnetic studies.