The design and synthesis of a novel type of self-assembled ionic composite composed of negatively charged Zn(salen) complexes and triphenylmethane derived polycations is reported. These composites were applied as easily recyclable catalysts for carbon dioxide addition to epoxides. The composites functioned as bifunctional catalysts which could be easily separated and recycled by precipitation from the reaction mixture upon addition of tetrachloromethane. The same batch of the catalyst could be employed for, at least, five runs with its catalytic properties improving as it was reused. A fully heterogeneous system was also prepared by cross-linking leuco dye with para-dibromoxylene and adding to it calculated amounts of Zn(salen) complex. The heterogeneous system was catalytically competent in the reaction between styrene oxide and carbon dioxide and its activity also increased on its reuse. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim