A highly efficient gas sensor is described based on the use of a nanocomposite fabricated from poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS) and ultra-large graphene oxide (UL-GO). The nanocomposite was placed by drop casting in high uniformity on interdigitated gold electrodes over a large area of silicon substrate and investigated for its response to volatile organic compounds (VOCs) at room temperature. Monolayers of ULGOs were synthesized based on a novel solution-phase method involving pre-exfoliation of graphite flakes. The nanocomposite was optimized in terms of composition, and the resulting vapor sensor (containing 0.04 wt% of UL-GO) exhibits strong response to various VOC vapors. The improved gas-sensing performance is attributed to several effects, viz. (a) an enhanced transport of charge carriers, probably a result of the weakening of columbic attraction between PEDOT and PSS by the functional groups on the UL-GO sheets; (b) the increase in the specific surface area on adding UL-GO sheets; and (c) enhanced interactions between the sensing film and VOC molecules via the network of π-electrons. The sensitivity, response and recovery times of the PEDOT-PSS/UL-GO nanocomposite gas sensor with 0.04 wt% of UL-GO are 11.3 %, 3.2 s, and 16 s, respectively. At a methanol vapor concentration as low as 35 ppm, this is an improvement by factors of 110, 10, and 6 respectively, compared to a PEDOT-PSS reference gas sensor without UL-GO.