The enhancement of grain refining action by the addition of boron along with titanium in aluminium and aluminium alloys is well known. This paper describes a process for the development of Al–5%Ti–1%B master alloy by the alloying of aluminium with titanium and also with boron which was produced in situ by the reduction of KBF4 with excess aluminium. Alloying efficiencies as high as 92 and 80%, respectively, for titanium and boron computed on the basis of elemental recovery were obtained at 1200°C. The decrease in grain size of aluminium by the addition of a calculated quantity of master alloy was also studied.