The electron and hole avalanche multiplication characteristics have been measured in bulk AlAs0.56Sb0.44 p-i-n and n-i-p homojunction diodes, lattice matched to InP, with nominal avalanche region thicknesses of ~0.6 μm, 1.0 μm and 1.5 μm. From these and data from two much thinner devices, the bulk electron and hole impact ionization coefficients (α and β respectively), have been determined over an electric-field range from 220-1250 kV/cm for α and from 360-1250 kV/cm for β for the first time. The α/β ratio is found to vary from 1000 to 2 over this field range, making it the first report of a wide band-gap III-V semiconductor with ionization coefficient ratios similar to or larger than that observed in silicon.