Metal-semiconductor junctions and interfaces have been studied for many years due to their importance in applications such as semiconductor electronics and solar cells. However, semiconductor-metal networks are less studied because there is a lack of effective methods to fabricate such structures. Here, we report a novel Au-ZnO-based metal-semiconductor (M-S)n network in which ZnO nanowires were grown horizontally on gold particles and extended to reach the neighboring particles, forming an (M-S)n network. The (M-S)n network was further used as a gas sensor for sensing ethanol and acetone gases. The results show that the (M-S)n network is sensitive to ethanol (28.1 ppm) and acetone (22.3 ppm) gases and has the capacity to recognize the two gases based on differences in the saturation time. This study provides a method for producing a new type of metal-semiconductor network structure and demonstrates its application in gas sensing.