Pseudomorphic GaAs1-ySby quantum wells with 0.16 <= y <= 0.69 on (0 0 1) InP substrates have been grown using metal-organic chemical vapour deposition. High resolution x-ray diffraction and transmission electron microscopy analysis are used to quantify the layer thicknesses and compositions. Studies of the optical properties suggest that a transition from type-I to type-II band alignment occurs at an antimony concentration of approximately y = 0.30. The interband optical transition energies simulated using a ten-band k · p Hamiltonian are compared with the experimental values deduced from photoluminescence spectroscopy. The valence band offset bowing parameter is evaluated in the context of the experimental transition energies. For low Sb-contents, reasonable agreement (<7% deviation) is achieved between theory and experiment for the primary optical transitions. However, at higher Sb-content, there is significant deviation between the measured transition energies and the k · p based theory, possibly a result of a non-ideal interface and/or heterogeneous ternary well.