In this research, ultraviolet laser-assisted atom-probe tomography (APT) was utilized to investigate precisely the behavior at the atomistic level of aluminum impurities in ultrathin epitaxial silicon layers. Aluminum atoms were incorporated in situ during the growth process. The measured average aluminum concentration in the grown layers exceeds by several orders of magnitude the equilibrium bulk solubility. Three-dimensional atom-by-atom mapping demonstrates that aluminum atoms precipitate in the silicon matrix and form nanoscopic precipitates with lateral dimensions in the 1.3 to 6.2 nm range. These precipitates were found to form only in the presence of oxygen impurity atoms, thus providing clear evidence of the longhypothesized role of oxygen and aluminum-oxygen complexes in facilitating the precipitation of aluminum in a silicon lattice. The measured average aluminum and oxygen concentrations in the precipitates are ∼10 ± 0.5 at.% and ∼4.4 ± 0.5 at.%, respectively. This synergistic interaction is supported by first-principles calculations of the binding energies of aluminum-oxygen dimers in silicon. The calculations demonstrate that there is a strong binding between aluminum and oxygen atoms, with Al-O-Al and O-Al-Al as the energetically favorable sequences corresponding to precipitates in which the concentration of aluminum is twice as large as the oxygen concentration in agreement with APT data.