Electroactive graft copolymers with different length and number of branches, poly(vinyl carboxy ethyl ether)-g-poly(pyrrole)s [PVCEE-g-(PPy)s] were able to be prepared according to the following steps; PVCEE was synthesized by reacting poly vinyl alcohol (PVA) with 3-chlolopropionic acid (CPA). Poly(vinyl pyrrolyl propanone ether) (PVPPE) was synthesized by fully or partially substituting carboxyl groups of PVCEE via carbonyl chloride groups with carbonyl pyrrolyl groups. Fully or partially substituted pyrrolyl groups in PVPPE act as the nuclei for electrochemical polymerization of pyrrole. Electroactive graft copolymers with different number of branches and length of pyrrolyl groups were finally obtained by keeping the total number of repeating groups of all branches constant on electrochemical polymerization of pyrrole on pyrrolyl groups of PVPPE. The differences of electrochemical properties and electroconductivity of these PVCEE-g-(PPy)s were investigated using cyclic voltammetry (CV) and chronoamperometry (CA). Synthesis of PVCEE-g-(PPy)s was characterized using FT-IR spectroscopy and (1)H-NMR.