In this paper, a novel strategy with a new growth mechanism for fast and large-scale growth of Au long nanowires on high-curvature SiO2 nanospherical surfaces has been developed. The synthesis includes three steps, i.e., amino modification of SiO2 nanospheres, Au seed loading on aminated SiO2 nanospheres and subsequently, Au seed-mediated nanowire growth on SiO2 nanospheres. The prepared Au nanowires (Au NWs) (exhibit long length, high aspect ratio, and good flexibility, and can naturally form the dense nanowire film, which is promising as a stable conductive electrode. In addition, the effect of synthetic conditions such as reactant feeding order, Au seeds and SiO2@Au seeds on the morphology of Au nanostructures (nanowires, nanoteeth, and nanoflowers) has been investigated. It is found that Au seeds and high-curvature SiO2 nanospherical surfaces are necessary conditions for the successful preparation of Au NWs and nanowire films. The different growth mechanisms for Au NWs and nanoteeth have been proposed and discussed. Moreover, the novel nonenzymatic H2O2 sensor based on Au NWs exhibits much enhanced performance such as higher sensitivity, stability, and selectivity, wider linear range and lower detection limit, compared with that of Au nanoparticles-based H2O2 sensor.