An etheric member of N-linked polybispyrroles (PolybisPy) based on 1-(3-(2-(2-(3-(1H-pyrrol-1-yl)propoxy)ethoxy)ethoxy)propyl)-1H-pyrrole (1) was electrochemically synthesized for the versatile investigation of its exciting electrochromic and ion receptor properties. It has been fully characterized by electroanalytic, spectroscopic, thermal, and four-probe techniques. It was thereby found that P1 shows strong stability, and a reversible redox process as well as a good electrochromic material property; transparent yellow in the neutral state, light pink in the intermediate state, and blue in the oxidized state. Also, the corresponding polymer (P1) exhibited a selective voltammetric response towards Na+ among the alkali series in an organic medium. Moreover, P1 film was employed for the detection of Ag+ ions in the solution with cyclic voltammetry without precipitants or complexing ligands, and SEM images confirmed the deposition of metallic silver on the film surface. These prominent features also make P1 a good candidate for many practical uses, such as the recovery of metals and ion sensors.