High-quality free-standing poly(dibenzo-18-crown-6) (PDBC) films with a conductivity of 4.1×10 −2 Scm −1 and good thermal stability were synthesized electrochemically on stainless steel electrode by direct anodic oxidation of dibenzo-18-crown-6 (DBC) in pure boron trifluoride diethyl etherate (BFEE). In this medium, the oxidation potential onset of DBC was measured to be only 0.98V vs. SCE, which was much lower than that in acetonitrile+0.1molL −1 Bu 4 NBF 4 (1.45V vs. SCE). PDBC films obtained from this medium showed good redox activity and stability in BFEE. The structural characterization of PDBC was performed using UV–vis, FTIR spectroscopy. The results of quantum chemistry calculations of DBC monomer and FTIR spectroscopy of PDBC films indicated that the polymerization mainly occurred at C (4) and C (5) positions). Fluorescent spectral studies indicated that PDBC was a blue light emitter. To the best of our knowledge, this is the first report on the electrodeposition of free-standing PDBC films.