[Abstract]: With the increasing use of fibre reinforced polymer (FRP) composites in civil engineering structures, there is a growing realisation of the need to develop newstructural systems which can utilise the unique characteristics of these materials in a more efficient and economical manner. In many instances this will require thedevelopment of new materials tailored to address the unique performance and economic parameters of mainstream construction. Over recent years, researchers at the University of Southern Queensland have pioneeredthe use of a new type of particulate filled polymer core material which greatly improves the robustness and cost effectiveness of FRP structural systems. These compositematerials are composed of small hollow spherical fillers (microspheres) in a thermosetting polymer matrix. Initial research into these materials, including theirfeasibility in prototype structural elements, have shown these materials to have major potential for widespread application in structural composite systems.One of the most promising classes of these materials investigated to date are vinyl ester / cenosphere composites, which utilise cenospheres derived from fly ash in a vinyl ester matrix. Previously reported studies into these materials have been restricted to initialsurveys of material behaviour which sought to identify key parameters in achieving desired performance outcomes in the composite. This dissertation presents the first in-depth investigation of these materials specifically as a core material option for civil infrastructure applications. The particular focus of this work is on the relationship of the vinyl ester matrix to the characteristics of the resultingcomposite. Several key matrix parameters were identified and assessed as to their influence on cure characteristics, fabrication operations, mechanical properties and theretention of such properties under elevated service temperatures. The outcomes of this work have significantly improved the understanding of matrix influences on the behaviour of these composite systems and have been drawn together to provide a number of recommendations on the application of this new technology to new structural systems.