The electrical conductivity can be significantly improved by constructing a three-dimensional conductive network through the chemical bonding of highly conductive one-dimensional AgNWs with two-dimensional GO. To achieve this, under acidic conditions and catalytic action at temperatures, the carboxyl group of mercaptoacetic acid undergoes esterification reaction with the hydroxyl group on GO. This reaction introduces a sulfhydryl group onto the surface of GO, resulting in the formation of graphene oxide bearing a sulfhydryl group, denoted as GO-SH. Subsequently, these sulfhydryl groups serve as growth sites for silver crystal species, allowing for precise control over the distribution and arrangement of AgNWs. The oriented arrangement of AgNWs enabled the successful preparation of AgNWs/ GO-SH composites with high electrical conductivity. Following this, the composites underwent comprehensive analysis of their structure and morphology using various characterization tools. The composite coatings prepared by vacuum filtration and mechanical pressing exhibited excellent electrical conductivity (2275.4 S/cm), as well as superior electromagnetic shielding properties (SE, 65.23 dB). These findings suggest promising applications in the field of electromagnetic shielding.