A Ga(AsBi) quantum well (QW) with Bi content reaching 6% and well width of 11 nm embedded in GaAs is grown by molecular beam epitaxy at low temperature and studied by means of high-resolution x-ray diffraction, photoluminescence (PL), and time-resolved PL. It is shown that for this growth regime, the QW is coherently strained to the substrate with a low dislocation density. The low temperature PL demonstrates a comparatively narrow excitonic linewidth of ∼ 40 meV. For high excitation density distinct QW excited states evolve in the emission spectra. The origins of peculiar PL dependences on temperature and excitation density are interpreted in terms of intra-well optical transitions.