X-ray photoelectron spectroscopy (XPS), laser ionisation mass analysis (LIMA) and X-ray diffraction (XRD) have been used to investigate composition, occurrence and association of mineral species on polished, fractured and powder surfaces of an Australian bituminous coal from the Whybrow seam, Saxonvale Colliery, New South Wales. XPS on raw coal samples revealed composition and the likely mineral types present which were concentrated predominantly in different bands of the coal. This was further confirmed using a new rapid and selective LIMA experimental method which is devised and optimised for in situ mineral particle identification. A series of mineral species occurring as fine, distributed inclusions were rapidly identified using LIMA, including quartz, pyrite, and a number of clays and carbonates. In addition, evidence for organic and inorganic sulfur species and some trace elements were also obtained from individual particles. Mineral identifications were confirmed by ashing the samples and analysis using XRD. This work highlights the advantages of using XPS and LIMA as complementary methods for coal mineral study.