The optical properties of GaAs epilayers grown by organometallic vapour phase epitaxy (OMVPE) on (001) Si substrates are reported. An increase in GaAs layer thickness led to an increase in photoluminescence (PL) intensity, a decrease in the full width at half-maximum (FWHM) of the excitonic transitions and an increase in the ratio of the exciton to carbon impurity peak heights. The best PL response (i.e., greatest intensity, smallest FWHM and lowest impurity concentration) was obtained from layers in which the initial Al0.2Ga0.8As nucleation layer was deposited at a low V/III ratio of 10. It was also shown that postgrowth thermal annealing and the incorporation of AlGaAs/GaAs superlattices resulted in a dramatic improvement in the optical quality of GaAs/Si epilayers.