We present 27Al and 29Si magic angle spinning nuclear magnetic resonance (MAS-NMR) spectra of Al- and Fe-bearing, high-pressure pyroxene and perovskite samples, synthesized in a multi-anvil apparatus at 26 GPa and 1900 °C at targeted compositions of (Mg1−xFex)(Si1−xAlx)O3 (x = 0.01, 0.025, and 0.05). 27Al MAS-NMR spectra of the perovskite samples indicate that Al3+ replaces both Si4+ in the octahedral site and Mg2+ in the larger 12-coordinated site. NMR signal loss caused by paramagnetic interactions is often a severe complication when performing NMR on materials containing Fe2+,3+; however, careful measurement of signal loss and comparison to total Fe content in these samples sheds light on the nature of Al and Fe incorporation. NMR signal loss for the pyroxenes is linearly related to total Fe content as would be expected in the case of uncorrelated substitution of randomly distributed Al and Fe. However, 27Al signal loss for the perovskite samples increases only slightly between samples with x = 0.01 and 0.025 indicating similar coordination of Al by Fe and non-random distribution. Complete signal loss at Fe/(Fe + Mg) = 0.05 suggests the upper limit of Fe2+ and Fe3+ concentration at which useful NMR data can be obtained for this system.