Monolayer ultra-large graphene oxide (UL-GO) sheets with diameter up to about 100 μm were synthesized based on a chemical method. Transparent conductive films were produced using the UL-GO sheets that were deposited layer-by-layer on a substrate by the Langmuir-Blodgett (L-B) assembly technique. The films produced from UL-GO sheets with a close-packed flat structure exhibit exceptionally high electrical conductivity and transparency after thermal reduction. A remarkable sheet resistance of 605 -/sq at 86% transparency is obtained, which outperforms the graphene films grown on a Ni substrate by chemical vapor deposition. The technique used to produce transparent conductive films is facile, inexpensive and tunable for mass production.