Crystalline polythiophene (Pth) film was first electrochemically deposited onto a nickel substrate from freshly distilled BF3-diethyl ether (BFEE) solution containing 15 mM thiophene. The crystalline film was studied by the X-ray diffraction technique and it was found to be a monoclinic unit cell with parameters a = 0.624 nm, b = 0.593 nm, c = 0.596 nm, and beta = 103.6 degrees. The film obtained from this medium has a compact morphology and great strength.