Previous experiments on Bx Ga1–x As containing a few percent boron show a dramatic increase in electron effective mass, m*e , similar to that observed in many GaNx As1–x samples. By contrast, there is a near‐linear blue‐shift of the energy gap, which can be conventionally described using the virtual crystal approximation. We use a tight‐binding model to show that isolated B atoms have little effect either on the band gap or lowest conduction band dispersion in Bx Ga1–x As. By contrast, B pairs and clusters introduce defect levels close to the conduction band edge (CBE) which, through a weak band‐anticrossing (BAC) interaction, significantly reduce the band dispersion in and around the Γ ‐point, thus accounting for the strong increase in m*e and reduction in mobility observed in these alloys. Calculations show that replacing gallium by aluminium shifts the CBE upwards, leading to a large density of B‐related states in the energy gap. By contrast, indium shifts the band edge downwards, leading eventually to a band edge m*e close to that predicted by the virtual crystal approximation. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)