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Stable thin films made from polyionic complex 2C12N+ PVS- with incorporated Hb on PG electrodes were characterized by electrochemistry. The electron transfer between Hb and PG electrodes was greatly facilitated in microenvironment of 2C12N+ PVS- films. The Hb-2C12N+ PVS- films could be used to catalytically reduce trichloroacetic acid.