Three trialuminide alloys, binary Al–25Sc, ternary Al–25Zr–6Fe, and quaternary Al–23Ti–6Fe–5V, all having the cubic L12 structure, were investigated. All three alloys fracture in a brittle manner (fracture toughness, 2–3 MPa m½), predominantly by transgranular cleavage. Of nineteen cleavage facets examined in binary Al3Sc, seventeen were of the {110} type and only two were of the {100} type, consistent with our earlier work which showed that the cleavage plane occurring most frequently in quaternary Al–23Ti–6Fe–5V is also {110}. The room-temperature hardnesses and yield strengths (100–200 DPH and 100–270 MPa, respectively) of all three alloys are quite low (comparable to ductile L12 alloys like Ni3Al), indicating that there is significant dislocation activity in these materials. Consistent with this, transmission electron microscopy identified several APB-coupled dislocations with b - a/2〈110〉 gliding on the {111} planes in both binary Al–25Sc and quaternary Al–23Ti–6Fe–5V. The separations between the superpartials in Al–25Sc and Al–23Ti–6Fe–5V were measured to be 3.7 and 4 nm, respectively, giving APB energies of 313 and 274 mJ/m2, respectively. Auger analyses failed to detect any impurities on the cleavage facets themselves, or on second phase particles (or other potential cleavage crack nucleation sites). It is therefore concluded that brittle fracture in these alloys is not impurity-induced. Based on all the results obtained to date we conclude that the unusual brittleness of L12 trialuminides is related to their intrinsically low cleavage strength. Possible reasons for their low cleavage strength are discussed.