Abstract(18‐Crown‐6)‐bridged phthalocyanine network polymers 4–8 as well as a low‐molecular‐weight model compounds with only one phthalocyanine unit (3a, b) were prepared from tetracyanodibenzo‐18‐crown‐6 (2a). The cyano end groups were partially converted into imido groups during the cyclotetramerization reaction, as detected from the IR spectra. In order to obtain structurally uniform compounds with the same end groups, the C N groups were hydrolyzed into imido groups with conc. sulfuric acid. The metal‐free phthalocyanine polymer 4a was obtained by the reaction of 2a either with hydroquinone or PbO in ethylene glycol. The chlorides of Cu(II), Ni(II), and Co(II) were empolyed in order to synthesize the corresponding metal‐phthalocyanine polymer, and Fe(CO)5 was used for the preparation of the Fe‐analog 7a. For the preparation of the Co‐containing polymer 8a ammonium molybdate has to be added as catalyst. The selectivity of 7a for Rb+ was found to be highest in the heterogeneous phase extraction experiments. Polymers 4–8 are also capable of binding silver from aqueous and methanolic solutions.