A micro-porous network thin film of core-tetrachlorinated perylene bisimide (PBI) was deposited by electrochemical polymerization, which showed reversible n-doping/dedoping processes at rather low potentials, accompanied by color changes from an orange red (neutral) state to a transparent (radical anion) state and further to an aquamarine (dianion) state. The film possesses preferable coloration efficiency and cycling stability (>10 000 cycles).