Replacement phenomena in amblygonite–montebrasite in rare-element pegmatites from the Karibib-Usakos area, Namibia, have been investigated using the electron microprobe. The first African occurrence and analysis of the very rare mineral natromontebrasite NaAl(PO4)(OH,F) is reported from the Daheim pegmatite. In the Okatjimukuju pegmatite, montebrasite has been replaced by a number of phases including crandallite CaAl3(PO4)2(OH)5·H2O and brazilianite NaAl3(PO4)2(OH)4. In one example, montebrasite has been almost completely replaced by brazilianite which has also been found to contain not only crandallite but also its solid solution analogues: goyazite SrAl3(PO4)2(OH)5·H2O and gorceixite BaAl3(PO4)2(PO3OH)(OH)6. Apatite is common at the contacts with montebrasite and associated minerals and texturally is intimately intergrown with crandallite, goyazite and gorceixite at Okatjimukuju. The occurrence of these minerals offers insight into the chemistry of post-magmatic fluids in these pegmatites.