Four dithiocarbamic polymers have been prepared by reacting a linear poly(ethylenimine) polymer (MW 50 000) with CS2. Depending on the reaction conditions the resulting polymeric products contained, up to two sulfur atoms per one nitrogen atom (similar to40% w/w). These polymers are soluble in dimethylsulfoxide and insoluble in acetonitrile solutions. In both solvents they are electrochemically active, in the latter case as cast film on glassy carbon or platinum electrodes. Specifically, upon oxidation the polymers turn into highly crosslinked (S-S bonds) form. The crosslinked polymer preserves partial electroactivity, although lower than expected due to its rigid structure but, more importantly, it is permeable to solvents and can act as an active matrix for electroactive species from the bulk solution. The switch between anionic and non-ionic (crosslinked) forms of the dithiocarbamic polymer results in transport of the solvent and lithium counterions between the film and the bulk solution.