Hole concentrations in excess of 1020cm−3have been achieved in AlxGa1−xAs using carbon doping during metalorganic molecular beam epitaxy. Hall and secondary‐ion mass spectrometry measurements show a 1:1 correspondence between the hole density and carbon concentration in as‐grown samples, although post‐growth annealing at 900 °C leads to a reduction in the net free‐carrier concentration (typically a decrease of ∼40% for 30 s anneals). The carbon‐localized vibrational modes (LVMs) show fine structure due to the presence of three different symmetries for substitutional carbon CAs, namelyTd, C2v, and C3v. The experimental CAsLVM line positions are in remarkable agreement with the predictions of a rigid ion model.