Zeolites have exceptional catalytic performance in oil refining and chemical synthesis that can be attributed to their well-defined porous structures that host active sites. This study pinpoints the exact locations of aluminum atoms in ZSM-5 structures—a key zeolite catalyst. Aluminum siting governs catalytic efficiency in acid and redox processes. Anomalous x-ray powder diffraction (AXRPD) at the aluminum K-edge probes the long-range order of aluminum atoms within the ZSM-5 frameworks, precisely quantifying both isolated aluminum atoms and Al(-O-Si-O-)xAl sequences (aluminum pairs). Supported by nuclear magnetic resonance studies, AXRPD unambiguously determines the crystallographic organization of aluminum pairs, recognized spectroscopically as α, β, and γ sites, linking their distribution to superior catalytic activity in propene oligomerization. This combined approach provides essential insights for optimizing zeolite catalysts and enhancing their performance.