Water availability is one of the most important factors limiting photosynthetic assimilation of carbon dioxide and growth of individual plants in terrestrial ecosystems. It is especially important for desert shrubs because the diurnal water availability is particularly sensitive to climate change in arid ecosystems. Water use efficiency (WUE) is an indicator of water availability and is frequently used to assess plant performance in various ecosystems, particularly in arid ecosystems. The WUE of plants has been widely assessed using ecological methods and field measurements; however, these approaches are impractical to obtain numerous near-simultaneous estimates of plant water status at the landscape-scale. Consequently, landscape-scale assessments of plant water status are practically pursued through modeling. In this study, measurement and modeling of the diurnal variations of WUE were conducted for a native dominant desert shrub, Tamarix ramosissima, in its original habitat on the periphery of the Gurbantunggut Desert, China. The diurnal net photosynthesis (A_n), stomatal conductance (g_s), and transpiration (T_r) were measured for each individual using a portable photosynthesis system. A coupled model of stomatal conductance, photosynthesis, and transpiration was applied to simulate the diurnal dynamics of A_n, g_s, T_r, and WUE. The model explained 83, 47, 83, and 55% of the variance in the measured A_n, g_s, T_r, and WUE values, respectively, for this desert ecosystem in which T. ramosissima is sparsely distributed. The results demonstrated that the coupled photosynthesis-stomatal conductance-transpiration model strategy is a promising approach to estimate water availability in desert ecosystems in Central Asia.