This paper presents a novel suction-controlled chamber that permits the determination of the full water retention curves of geosynthetic clay liners (GCLs) under non-uniform temperature-stress paths. It investigates field conditions encountered in brine ponds (low confining stress settings) and heap leach pads (high confining stress settings) during construction and operation stages. Consequently, the analysis of the moisture dynamics in a GCL was defined under the wetting path (construction) and drying path (operation). High vertical stresses were found to facilitate a more rapid water uptake as capillarity is established faster than at low, confined stresses. In general, the drying curves increase the water desorption over the suction range investigated due to the low water viscosity caused by high temperatures. The wetting of the GCL at 20 °C and drying at 70 °C under either low, confined stress (2 kPa) or high confining stress (130 kPa) shows a reduction in the volumetric water contents. Furthermore, on the drying path, the coupled effect of elevated temperature and high confining stress accelerates water desorption leading possibly to potential desiccation.