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Optically detected X-ray absorption spectroscopy (ODXAS) and X-ray excited optical luminescence (XEOL) have been applied in parallel to the study of local bonding in luminescent diamonds. Imaging ODXAS and XEOL reveal correlations between lateral variation in colour (transmitted light and luminescence) and local carbon bonding in selected samples showing strong optical absorption contrast. Dark regions of the crystals viewed in transmitted light correlate with a lower total luminescence yield when excited with soft X-rays of photon energy ~280 eV. ODXAS reveals a higher proportion of sp2-bonded carbon species in darker (less luminescent) regions associated with graphitic micro-inclusions.