Spectroscopic ellipsometry from 1.4 to 5 eV was used to systematically characterize epitaxial heterostructures AlxGa1-xSb/GaSb for different x concentrations (x≤0.5). The structures were grown by MBE at temperatures and beam equivalent pressure ratios which optimize their lowtemperature photoluminescence properties. Complex dielectric functions of AlxGa1-xSb versus x were derived, for the first time, from the ellipsometric spectra after mathematically removing the oxide overlayer effects. The spectra were analyzed with their second energyderivatives in term of standard analytical lineshapes: in particular the El, E1+Δ1 and E2 critical point energies, broadening and amplitude parameters were derived as a function of x. On this basis we verified that the energy-shift model is appropriate to interpolate for any x≤0.5, thus allowing a nondestructive optical diagnostic of layer thickness and composition of epitaxial heterostructures based on A1xGa1-xSb.