We report the discrimination of Al doping sites in sol–gel-formed ZnO powders by solid-state 27Al nuclear magnetic resonance (NMR) spectrometry. A degree of control of dopant placement is demonstrated by modifying sol precursors and processing parameters. ZnO powders containing 1–8 at. % aluminum ions were prepared from aqueous citrate-amino-alcohol-based gels calcined at 500 °C. The powders were characterized using ²⁷Al NMR spectrometry, X-ray diffraction (XRD), and scanning electron microscopy (SEM). Solid-state ²⁷Al NMR spectrometry clearly distinguished between different Al environments and was effective in determining the relative amounts of incorporation of Al dopant ions into the Zn lattice sites in the zincite structure. This allowed a synthesis protocol to be developed to optimize the doping effectiveness. Relatively minor variations in processing conditions could influence the degree and mode of Al incorporation. Optimal conditions were found to include a 90 °C drying step, followed by placement in a preheated (500 °C) furnace for 1 h. An ethanolamine-containing precursor was shown to perform much better than precursors containing alternative amino alcohols.