This paper presents the results and interpretations of a pilot study of pigment characterisations conducted between 2002 and 2006 on the rock art assemblage of the south Woronora Plateau located immediately west of Wollongong, New South Wales. Eighteen samples from ten sites are described. Analyses of the geochemistry, mineralogy and micro-morphology of samples was undertaken using a combination of scanning electron microscopy including energy dispersive x-ray analysis, x-ray diffraction, particle induced x-ray emission and particle induced gamma-ray emission techniques. With one exception the analyses show that composite clay-based paints were used to produce both iconic and non-iconic rock art on the Woronora Plateau and adjacent Mittagong Tablelands. We discuss differences in the processing of paints used for iconographic and stencil art, and consider the possible chronological and behavioural implications of paint chemistry and morphology. The results of the study, while indicative, provide an exciting example of the type of archaeometric work which can be undertaken successfully in the taphonomically complex Hawkesbury Sandstone rockshelters of the Sydney Basin.