Constructed Technosols may be an alternative for creating urban green spaces. However, the hydro-structural properties emerging from the assembly of artefacts have never been documented. The soil shrinkage curve (SSC) could provide relevant structural information about constructed Technosols, such as the water holding capacity of each pore system (macropores and micropores). The objectives of this study were (i) to evaluate the SSC and water retention curve (WRC) to describe the structure of constructed Technosols and (ii) to understand the influence of organic matter content on soil hydro-structural properties. In this study, Technosols were obtained by mixing green waste compost (GWC) with the material excavated from deep horizons of soil (EDH). The GWC was mixed with EDH in six different volumetric percentages from 0% to 50% (GWC/total). The GWC and EDH exhibited highly divergent hydro-structural properties: the SSC was hyperbolic for GWC and sigmoid for EDH. All six mixture treatments (0%, 10%, 20%, 30%, 40% and 50% GWC) exhibited the classical sigmoid shape, revealing two embedded levels of pore systems. The 20% GWC treatment was hydro-structurally similar to the 30% and 40% GWC treatments; so, a large quantity of expansive GWC is unnecessary. The relation with the GWC percentage was a second-degree equation for volumetric available water in micropores, but was linear for volumetric available water in macropores and total volumetric available water. Total volumetric available water in the 50% GWC treatment was twice as high as that in the 0% GWC treatment. By combining SSCs and WRCs, increasing the GWC percentage increased water holding capacity by decreasing the maximum equivalent size of water-saturated micropores at the shrinkage limit and increasing the maximum equivalent size of water-saturated macropores, resulting in an increased range of pore diameter able to retain available water.