The results of photoluminescence measurements ofp‐type AlxGa1−xAs:Ge (with 0.03<x<0.39) grown by liquid phase epitaxy are presented. An investigation of the composition and temperature dependencies of the acceptor‐related peak in this range shows that Ge behaves as a shallow effective mass‐like center. The discontinuity in the variation in peak energy versus composition that occurs atx= 0.30 is explained rather in terms of a crossing of donor levels associated with the direct and indirect band gaps. It is also shown that the luminescence is characteristic of donor‐acceptor recombination involving shallow donors forx<0.30, whereas a deep donor or a vacancy complex is indicated forx≳0.30. The broad emission band at ∼1.5 eV has also been investigated but its source has not been identified. The presence of this band in the room temperature spectrum and the implications for characterization of light‐emitting devices are discussed.