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With the advent of modern microstructural testing techniques and microstructure based constitutive models the microstructural characterisation of soils is gaining prominence. This paper reviews the history of microstructure investigation in unsaturated soils and discusses the engineering significance of this research to date. After a brief overview of the main microstructural techniques, the paper focuses on the evaluation of the current state of use and the development of two widely used techniques to study the microstructure of partially saturated soils, namely mercury intrusion porosimetry and the environmental scanning electron microscopy. The details of these techniques, their advantages and limitations, are first covered, followed by the presentation of selected test results. These results highlight the use of these techniques for understanding different hydro-mechanical behavioural features observed at macroscopic scale. Specifically, the paper shows the use of these techniques to explore the fundamental properties of water retention characteristics, water permeability, and micro and macrostructural interactions along different hydro-mechanical paths.