Soft x‐ray photoelectron spectroscopy has been used to compare the chemistry of Al/InP(110) and Al/GaSe interfaces at room and low (<120 K) temperatures. For Al/InP(110) at low temperature it was found that the reacted feature of the In 4dspectrum has a coverage dependent binding energy. This is a result of the altered growth mode of the reacted In atoms on the low‐temperature surface. The spectral weight of the reacted feature is shown to be equivalent at the two temperatures, but escape depth effects imply that some reduction in reactivity has occurred. The behavior of the Al/GaSe interface is quite different. At low temperature no evidence for reaction was found within the equivalent coverage range. These results are discussed within the cluster‐initiated exchange reaction model.