An aluminum matrix syntactic foam, incorporated with hollow-structured fly ash particles, was fabricated by pressure infiltration technique. X-ray micro-computed tomography was used to characterize its heterogeneous microstructure three dimensionally (3D). The quantification of some microstructure features, such as content and size distribution of hollow fly ash particles, was acquired in 3D. The tomographic data were exploited as a rapid method to generate a microstructurally accurate and robust 3D meshed model. The thermal transport behavior has been modeled using a commercial finite-element code to conduct steady state analyses. Simulation of the thermal conductivity showed good correlation with experimental result.