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Soil salinization has become one of the main factors restricting sustainable development of agriculture. Field spectrometry provides a quick way to predict the soil salinization. However, soil moisture content (SMC) seriously interferes with the spectral information of saline soil in arid areas. It is vital to establish a model that is insensitive to SMC for potential in situ field applications. The soil spectral reflectance exponential model (SSREM) has been widely employed for reflectance simulation and SSC inversion. However, its reliability for saline soils with high SMC has not been verified yet. Based on hyperspectral remote sensing data (400~1000 nm) on 459 saline soil samples in Shiyang River Basin of Northwest China, we investigated the role of SMC and SSC in soil spectral reflectance from 29 October 2020 to 22 January 2021. Targeted at saline soils, soil spectral moisture threshold (MT) was introduced to improve the SSREM toward a modified spectral reflectance exponential model (MT-SSREM). The bands that are sensitive to SSC but not sensitive to SMC were obtained based on a method of correlation analysis between original spectra, four kinds of spectral data, and SSC. SSREM and MT-SSREM were finally applied to inversely estimate SSC. Results show that wavelengths at 658~660, 671~685, 938 nm were suitable for SSC estimation. Furthermore, although SSREM was able to simulate the spectral reflectance of most saline soils, its simulation accuracy was low for saline soil samples with high SMC (SMC > MT(i), 400 nm ≤ i ≤ 1000 nm), while MT-SSREM performed well over the whole range of SMC. The simulated spectral reflectance from MT-SSREM agreed well with the measured reflectance, with the R2 being generally larger than 0.9 and RMSE being less than 0.1. More importantly, MT-SSREM performed substantially better than SSREM for SSC estimation; in the statistical performance of the former case, R2 was in range of 0.60~0.66, RMSE was in range of 0.29~0.33 dS m−1; in the latter case, R2 was in range of 0.10~0.16, RMSE was in the range of 0.26~0.29 dS m−1. MT-SSREM proposed in this study thus provides a new direction for estimating hyperspectral reflectance and SSC under various soil moisture conditions at wavelengths from 400 to 1000 nm. It also provides an approach for SSC and SMC mapping in salinization regions by incorporating remote sensing data, such as GF-5.