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.