As a special type of clay, expansive clay is widely distributed in China. Its characteristics of swelling and softening when meeting water and shrinking and cracking when losing water bring many hidden dangers to engineering construction. Expansive clay is known as “engineering cancer”, and in-depth research on the unloading mechanical response characteristics and the unloading constitutive relationships of expansive clay is a prerequisite for conducting geotechnical engineering design and safety analysis in expansive-soil areas. In order to obtain the unloading mechanical response characteristics and the expression of the unloading tangent modulus of expansive clay, typical expansive clay in the Hefei area was taken as the research object, and triaxial unloading stress path tests were conducted. The stress–strain properties, microstructures, macro failure modes, and strength indexes of the expansive clay were analyzed under unloading stress paths. Through an applicability analysis of several classical soil strength criteria, an unloading constitutive model and the unloading tangent modulus expression of the expansive clay were constructed based on the Mohr–Coulomb (hereinafter referred to as “M-C”) criterion, the Drucker–Prager (hereinafter referred to as “D-P”) criterion, and the extended Spatial Mobilized Plane (hereinafter referred to as “SMP”) criterion theoretical frameworks. The following research results were obtained: (1) The stress–strain curves of the three stress paths of the expansive clay were hyperbolic. The expansive clay showed typical strain-hardening characteristics and belonged to work-hardening soil. (2) Under the unloading stress paths, the soil particles were involved in the unloading process of stress release, and the failure samples showed obvious stretching, curling, and slipping phenomena in their soil sheet elements. (3) Under both unloading stress paths, the strength of the expansive clay was significantly weakened and reduced. Under the lateral unloading paths, the cohesive force (c) of the expansive clay was reduced by 32.7% and the internal friction angle (φ) was increased by 19% compared with those under conventional loading, while under the axial unloading path, c was reduced by 63.5% and φ was reduced by 28.7%. (4) For typical expansive clay in Hefei, the conventional triaxial compression (hereinafter referred to as “CTC”) test, the reduced triaxial compression (hereinafter referred to as “RTC”) test, and the reduced triaxial extension (hereinafter referred to as “RTE”) test stress paths were suitable for characterization and deformation prediction using the M-C strength criterion, D-P strength criterion, and extended SMP strength criterion, respectively. (5) The derived unloading constitutive model and the unified tangent modulus formula of the expansive clay could accurately predict the deformation characteristics of the unloading stress path of the expansive clay. These research results will provide an important reference for future engineering construction in expansive-clay areas.