For the application of single-walled carbon nanotubes (SWNTs) to electronic and optoelectronic devices, techniques to obtain semiconducting SWNT (s-SWNT) arrays are still in their infancy. We have developed herein a rational approach for the preferential growth of horizontally aligned s-SWNT arrays on a ST-cut quartz surface through the selective scission of C-O and C-C bonds of ethanol using bimetal catalysts, such as Cu/Ru, Cu/Pd, and Au/Pd. For a common carbon source, ethanol, a reforming reaction occurs on Cu or Au upon C-C bond breakage and produces C(ads) and CO, while a deoxygenating reaction occurs on Ru or Pd through C-O bond breaking resulting in the production of O(ads) and C2H4. The produced C2H4 by Ru or Pd can weaken the oxidative environment through decomposition and the neutralization of O(ads). When the bimetal catalysts with an appropriate ratio were used, the produced C(ads) and C2H4 can be used as carbon source for SWNT growth, and O(ads) promotes a suitable and durable oxidative environment to inhibit the formation of metallic SWNTs (m-SWNTs). Finally, we successfully obtained horizontally aligned SWNTs on a ST-cut quartz surface with a density of 4-8 tubes/μm and an s-SWNT ratio of about 93% using an Au/Pd (1:1) catalyst. The synergistic effects in bimetallic catalysts provide a new mechanism to control the growth of s-SWNTs.