In recent years there have been an increasing number of investigations aimed at ‘bridging the pressure gap’ between UHV surface science experiments on well-characterised single crystal surfaces and the much higher (ambient and above) pressures relevant to practical catalyst applications. By applying existing photon-in/photon-out methods and developing instrumentation to allow photoelectron emission to be measured in higher-pressure sample environments, it has proved possible to obtain surface compositions and spectroscopic fingerprinting of chemical and molecular states of adsorbed species at pressures up to a few millibars. None of these methods, however, provide quantitative structural information on the local adsorption sites of isolated atomic and molecular adsorbate species under these higher-pressure reaction conditions. Methods for gaining this information are reviewed and evaluated.