Granitic pegmatites are exceptional igneous rocks and the possible role of an immiscibility process in their origin is strongly debated. To investigate metal and metalloid behaviour in hydrous peraluminous systems (aluminium saturation index, ASI >1), we analysed 15 quartz-hosted primary melt and fluid inclusions from pegmatites in the Ehrenfriedersdorf Complex (Erzgebirge, Germany) and 26 primary melt inclusions from leucogranites of the Ehrenfriedersdorf district (Germany), Kymi (Finland) and Erongo (Namibia) by femtosecond laser ablation inductively coupled plasma quadrupole mass spectrometry. The results presented here for 32 elements provide evidence for metal and metalloid fractionation between two types of immiscible melts (A and B) and NaCl–HCl-rich brine in the pegmatite system. No evidence for the boundary layer effect was observed in the 40–500 μm size melt inclusions that were investigated. The data on the Ehrenfriedersdorf pegmatites allow quantification of the metal and metalloid partitioning between natural NaCl-rich brine and the two types of melt (e.g. ). These data are in accord with existing natural and experimental data on equilibrium fluid–melt partitioning as well as spectroscopic data on the metal and metalloid complexation in hydrous aluminosilicate melts and NaCl–HCl-rich fluids.