The pioneering study of Shimizu et al. (J. Anal. At. Spectrom., 2004, 19, 692) on the examination of adsorbed organic molecules on a copper substrate by radio frequency glow discharge optical emission spectrometry (rf-GDOES) displayed the potential of GDOES for determination of the orientations of molecular monolayers. Here, the study has been extended to the examination of thiourea adsorbed on silver, gold and copper surfaces and metal-centred molecular wires (MCMWs) of 4-6 nm length, with cobalt atoms in the middle of the chain adsorbed on a gold surface. According to established data, these molecules are adsorbed onto a metal surface through a sulphur atom. Depth profiling of thiourea adsorbed on the copper surface confirmed the results of Shimizu et al., with a nitrogen peak followed by a sulphur peak in the depth profile revealed with sputtering time. However, in the case of silver and gold substrates, the positions of the sulphur and nitrogen peaks in the depth profiles were not as predicted from the orientation of the thiourea molecule, i.e. the nitrogen peak followed the sulphur peak with sputtering time or the peaks overlapped. In the depth profiles of the adsorbed MCMWs, the sulphur peak appeared prior to the cobalt peak with sputtering time. Further, the time required for sputtering of thiourea and the wires are comparable, whereas the lengths of thiourea and the wire molecules differ by more than one order of magnitude. Thus, in this case, no correlation between the orientation of the molecules and the peak sequence in the depth profiles has been observed. This journal is © 2013 The Royal Society of Chemistry.