The ACGIH® Threshold Limit Value® (TLV®) is used to limit heat stress exposures so that most workers can maintain thermal equilibrium. That is, the TLV was set to an upper limit of Sustainable exposures for most people. This article addresses the ability of the TLV to differentiate between Sustainable and Unsustainable heat exposures for four clothing ensembles over a range of environmental factors and metabolic rates (M). The four clothing ensembles (woven clothing, and particle barrier, water barrier and vapor barrier coveralls) represented a wide range of evaporative resistances. Two progressive heat stress studies provided data on 480 trials with 1440 pairs of Sustainable and Unsustainable exposures for the clothing over three levels of relative humidity (rh) (20, 50 and 70%), three levels of metabolic rate (115, 180, and 254 Wm-2) using 29 participants. The exposure metric was the difference between the observed wet bulb globe temperature (WBGT) and the TLV. Risk was characterized by odds ratios (ORs), Receiver Operating Characteristic (ROC) curves, and dose-response curves for the four ensembles. Conditional logistic regression models provided information on ORs. Logistic regressions were used to determine ROC curves with area under the curve (AUC), model the dose-response curve, and estimate offsets from woven clothing. The ORs were about 2.5 per 1°C-WBGT for woven clothing, particle barrier, and water barrier and for vapor barrier at 50% rh. When using the published Clothing Adjustment Values (CAVs, also known as Clothing Adjustment Factors, CAFs) or the offsets that included different values for vapor barrier based on rh, the AUC for all clothing was 0.86. When the fixed CAVs of the TLV were used, the AUC was 0.81. In conclusion, (1) ORs and the shapes of the dose-response curves for the nonwoven coveralls were similar to woven clothing, and (2) CAVs provided a robust way to account for the risk of nonwoven clothing. The robust nature of CAV extended to the exclusion of different adjustments for vapor barrier by rh.