Excitonic optical properties of Ga-rich AlxGa1-xN ternary alloy epitaxial layers with aluminum compositions of x = 0.019, 0.038, 0.057, 0.077, and 0.092 have been studied by means of photoluminescence (PL), time-resolved PL, and PL excitation spectroscopy. The luminescence line due to radiative recombination of biexcitons was clearly observed for all of five samples. On the basis of two-photon absorption of biexcitons, a Stokes shift of biexcitons and binding energy of biexcitons were determined quantitatively as a function of aluminum composition. The biexciton localization due to alloy disorder resulted in a strong enhancement of the biexciton binding energy.