This paper is part of a systematic examination by the authors of Sydney's changing political economy within its largely self-imposed globalisation agenda. This part seeks to unravel the changing nature of Sydney's material connections across the Sydney basin economy and with other places. The analysis is based on novel uses of GIS-based software and its application to freight flow data. There are employed to describe and delineate the composition, intensity and direction of materials flows arising from the functioning of the Sydney economy. Two questions are explored. First, we seek to expose the global city metaphor as narrowly defining what Sydney is and how it operates economically. Second, and following Blomley's (2005) call for a new look of the idea of 'property', we undertake a resurrection of the materials sector of the economy as having important political presence. Here we ask: what is the substance of a material such that it is worth moving? how are materials politicised by their generation, distribution and appropriation? how do spatial contexts influence the ways materials are valued and assigned meaning? and what is the role of materials in deterritorialising and reterritorialising urban economies. Of course, this privileging of materials flows deliberately holds back the presence of the services, property and finance sectors. We reserve these for later analysis.