In the present study, the one‐dimensional ZnO nanorod structures are produced within the different nickel and aluminum molecular weight ratios of 0–7% using the hydrothermal method. It is found that the aluminum (Al) and nickel (Ni) impurities with different ionic radius, chemical valence, and electron configurations of outer shell cause to vary the fundamental characteristic features including the crystallinity quality, crystallite size, surface morphology, nanorod diameter, optical absorbance, energy band gap, resistance, gas response, and gas sensing properties. The structural analyses performed by powder X‐ray diffraction (XRD) and scanning electron microscopy (SEM) indicate that the samples are found to crystallize in the hexagonal wurtzite structure. The presence of optimum nickel and aluminum in the crystal system improves considerably the crystallinity quality and surface morphology. Additionally, the combination of electron dispersive X‐ray (EDX) and XRD results declare that the Ni and Al impurities incorporate successfully into the ZnO crystal structure. Moreover, the diameters of nanorod structures in 1D orientation are determined to be 80 nm or below. The hexagonal wurtzite‐type ZnO nanorod structure prepared by 5% Ni has more space between the nanorods and thus presents higher response to the CO2 detection. Further, the optical absorbance spectra display that the band gap value is observed to decrease regularly with the increment in the doping level as a result of band shrinkage effect depending on the enhancement of mobile hole carrier concentrations in the crystal structure. In other words, the doping mechanism leads to vary the homogeneities in the interfacial charges, nanorod diameters, ZnO oxide layer composition and thickness. The last test conducted in this study is responsible for the determination of CO2 gas sensing levels. The obtained gas sensing results are further compared with each other and literature findings. It is observed that 5% Ni‐doped sample provides more successful results than other samples in the sensing CO2 gas at the different concentrations. All in all, the paper establishing a strong methodology between doping mechanism and change in the fundamental characteristic features of hexagonal wurtzite‐type ZnO with the aid of advanced microscopy techniques will become pioneering research to answer key questions in materials sciences and electronic research.