This paper summarises results of the epitaxial growth of Ga(NAsBi) by metal-organic vapour phase epiLaxy (MOVPE) and the subsequent optical and structural characterisations of the samples. Ga(NAsBi)/GaAs multi-quantum well (MQW) samples are grown at 400 degrees C and single layers at 450 degrees C on GaAs (001) substrates. Triethylgallium (TEGa), tertiarybutylarsine (TBAs), trimethylbismuth (TMBi) and unsymmetrical dimethylhydrazine (UDMHy) are used as precursors. Secondary ion mass spectrometry (SIMS) shows that the Bi content is independent of the N content in the alloy. It is found that the N content depends on both UDMHy and TMBi supply during growth. High resolution X-ray diffraction (HR-XRD), scanning transmission electron microscopy (STEM) and atomic force microscopy (AFM) measurements show that samples with good crystalline quality can be realised. For samples containing 1.8% Bi and up to 1.8% N grown at 450 degrees C, photorellectance spectroscopy (PR) shows a decrease in the band gap with increasing N content of 141 +/- 22 meVi% N. (C) 2014 Elsevier B.V. All rights reserved.