Living bifunctional azo-polytetrahydrofuran (azo-PTHF) was terminated with pyrrolyl potassium salt to yield a polymer with electrochemically active functional end groups. This polymer is further used to synthesize polytetrahydrofuran-polystyrene (PTHF-b-PS-b-PTHF) block copolymer. These polymers are electrochemically blocked with polypyrrole using constant potential electrolysis (PPy/Azo-PTHF and PPy/PTHF-b-PS-b-PTHF). Two different solvent-electrolyte pairs were used during electrolysis. Characterizations of pristine and the blocked copolpolymers are based on Cyclic Voltammetry (CV), Fourier Transform Infrared Spectroscopy (FTIR), Differential Scanning Calorimetry (DSC), Thermal Gravimetry Analysis (TGA), Scanning Electron Microscope (SEM) Nuclear Magnetic Resonance Spectroscopy (NMR) and Gel Permeation Chromatography (GPC). Conductivities were measured using a four-probe technique.