New insights into controlling boundary layer thickness are investigated in growth of Cr2O3- decorated ZnO multipods on a tilted silicon substrate. In the first step, ZnO multipods were grown on a tilted silicon surface using a vapor transport method in a quartz tube. Next step, low concentration of Cr2O3 nanoparticles was decorated on the ZnO multipods using a PVD machine. Both arm diameter and density of the Cr2O3- decorated ZnO multipods were found to be strongly dependent on the boundary layer thickness. The sensing properties of the samples measured by half bridge method indicated that decoration of the Cr2O3 nanoparticles on the ZnO multipods significantly enhanced the response to 100 ppm NH3 up to 85, CO2 up to 29 and NO2 up to 27. The response/recovery times were 25 s/48 s at 300 °C. Blue defect emission appeared in room temperature photoluminescence spectra of the sample grown in a thin boundary layer thickness.