It is demonstrated that reliable aluminum–carbon distances can be measured in samples with 13C natural abundance by NMR spectroscopy. Overcoupled resonators, with only one radio‐frequency synthesizer and one amplifier, are used to irradiate in the same pulse sequence 27Al and 13C nuclei, which differ by only 3.6 % in Larmor frequencies. The combination of 27Al saturation pulse with heteronuclear dipolar recoupling yields dipolar dephasing of the 13C signal, which only depends on the AlC distance and the efficiency of the saturation pulse. Therefore, reliable distances can be obtained by rapid fitting of experimental data to an analytical expression. It is demonstrated that with natural isotopic abundance this approach allows recovery of AlC distances of 216 pm for the covalent bond in lithium tetraalkyl aluminates, commonly used as a co‐catalyst in olefin polymerization processes, and which range from 274 to 381 pm for the three carbon atoms in aluminum lactate. The accuracy of the measured internuclear distances is carefully estimated.