The sonochemical process drives chemical reactions with sound fields by creating extraordinarily high density of energy, pressure and temperatures. The process resulted in a number of unexpected chemical species and thought-provoking results in the recent past. In this paper, we present a new sonochemical approach to synthesize ZnO (zinc oxide) nanowalls (NWalls) on aluminum and alumina coated substrates at room ambient conditions. We achieved highly dense and uniform ZnO NWalls in areas that are coated with Al or Al2O3 (alumina). The synthesis process was shown not to occur on Si, SiO2, Cr, or Ag surfaces. A series of experiments on understanding the growth kinetics offers detailed insight into the growth dynamics over time. Photoluminescence (PL) measurements, UV Vis spectroscopy, and SEM-EDS results confirm NWalls composed of crystalline ZnO that are formed via Al assisted growth induced by phase transformations under extraordinary pressure, temperature, and chemical growth kinetics. The chemical growth method as reported here, is applicable to arbitrary substrates coated with an Al thin film. We demonstrate the applications of the as-formed NWalls in UV photoconductors and gas sensors.