Brush-like ZnO hierarchical nanostructures decorated with MgxZn1-xO (x = 0.1, 0.2, 0.3, 0.4, and 0.5) were fabricated and examined for application to a gas sensor. They were synthesized using vapor phase growth (VPG) on indium tin oxide (ITO) substrates. To generate electronic accumulation at ZnO surface, MgZnO nanoparticles were prepared by sol-gel method, and the ratio of Mg and Zn was adjusted to optimize the device for NO2 gas detection. As the electrons in the accumulation layer generated by the heterojunction reacted faster and more frequently with the gas, the sensitivity and speed improved. When tested as sensing materials for gas sensors at 100 ppm NO2 at 300oC, these MgZnO decorated ZnO nanostructures exhibited an improvement from 165 to 514 times compared to pristine ZnO. The response and recovery time of the MgZnO decorated ZnO samples were shorter than those of the pristine ZnO. Various analyzing techniques, including field-emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDS), and X-ray powder diffraction (XRD) were employed to confirm the growth morphology, atomic composition, and crystalline information of the samples, respectively.