The relationship between the physic features of the Earth’s surface and its temperature has been significantly investigated for further soil moisture assessment. In this study, the spatiotemporal impacts of surface properties on land surface temperature (LST) were examined by using Landsat-8 Operational Land Imager (OLI) and Thermal Infrared Sensor (TIRS) and meteorological data. The significant distinctions were observed during a crop growing season through the contrast in the correlation between different multi-spectral satellite indices and LST, in which the highest correlation of −0.65 was found when the Normalized Difference Latent heat Index (NDLI) was used. A new index, named as Temperature-soil Moisture Dryness Index (TMDI), is accordingly proposed to assess surface moisture and evapotranspiration (ET) variability. It is based on a triangle space where NDLI is set as a reference basis for examining surface water availability and the variation of LST is an indicator as a consequence of the cooling effect by ET. TMDI was evaluated against ET derived from the commonly-used model, namely Surface Energy Balance Algorithm for Land (SEBAL), as well as compared to the performance of Temperature Vegetation Dryness Index (TVDI). This study was conducted over five-time points for the 2014 winter crop growing season in southern Taiwan. Results indicated that TMDI exhibits significant sensitivity to surface moisture fluctuation by showing a strong correlation with SEBAL-derived ET with the highest correlation of −0.89 was found on 19 October. Moreover, TMDI revealed its superiority over TVDI in the response to a rapidly changing surface moisture due to water supply before the investigated time. It is suggested that TMDI is a proper and sensitive indicator to characterize the surface moisture and ET rate. Further exploitation of the usefulness of the TMDI in a variety of applications would be interesting.