We investigated the effect of different spray-coating parameters on the electro-optical properties of Ag nanowires (NWs). Highly transparent and conductive Ag NW⁻graphene oxide (GO) hybrid electrodes were fabricated by using the spray-coating technique. The Ag NW percolation network was modified with GO and this led to a reduced sheet resistance of the Ag NW⁻GO electrode as the result of a decrease in the inter-nanowire contact resistance. Although electrical conductivity and optical transmittance of the Ag NW electrodes have a trade-off relationship, Ag NW⁻GO hybrid electrodes exhibited significantly improved sheet resistance and slightly decreased transmittance compared to Ag NW electrodes. Ag NW⁻GO hybrid electrodes were integrated into smart windows based on polymer-dispersed liquid crystals (PDLCs) for the first time. Experimental results showed that the electro-optical properties of the PDLCs based on Ag NW⁻GO electrodes were superior when compared to those of PDLCs based on only Ag NW electrodes. This study revealed that the hybrid Ag NW⁻GO electrode is a promising material for manufacturing the large-area flexible indium tin oxide (ITO)-free PDLCs.