Graphene oxide (GO) nanosheets are introduced to a Quaternized polyvinyl alcohol (QPVA) polymer matrix to obtain an anion exchange membranes (AEMs) for application of fuel cells. QPVA/GO nanocomposite membranes provide desirable properties such as low fuel uptake and permeability, excellent ionic conductivity, and cell performance, all of which are favorable for AEMs based on our previous works. Passive direct methanol fuel cells (DMFCs) are recognized as suitable technologies for use in portable devices. Nevertheless, the commercialization of DMFCs remains restricted due to a number of issues related to the conventional membrane; one of these issues is high fuel crossover problems due to high fuel uptake and permeability of Nafion membrane. This study aimed to expand the potential applications of QPVA/GO nanocomposite membranes in air-breathing passive DMFCs. The ionic conductivity, methanol uptakes (MUs), and permeabilities of self-synthesis QPVA/GO nanocomposites are examined to evaluate the ability to operate in methanol atmosphere. At 30 degrees C, the ionic conductivity of the membranes reached 1.74 x 10(-2)S cm(-1). The MUs and permeabilities were as low as 35% and 7.6 x 10(-7)cm(2)s(-1), respectively. The performance of air-breathing passive DMFCs bearing QPVA/GO nanocomposite membrane is much higher compared to conventional membranes. The maximum power density of air-breathing passive DMFCs was achieved 27.2 mW cm(-2)under the optimum condition of 2 M methanol + 4 M KOH at 70 degrees C. Single-cells could be sustained for 1000 hours. This article is the first to optimize and highlight the performance air-breathing passive DMFCs by using a QPVA-based membrane.