Canopy temperature has been proposed as a relevant variable for crop water stress monitoring. Since crop temperature is highly influenced by the prevailing climatic conditions, it is usually normalized with indices such as the crop water stress index (CWSI). The index requires the use of two baselines that relate canopy temperature under maximum stress and non-water stress conditions with vapor pressure deficit (VPD). These reference baselines are specific to each crop and climatic region. In maize, they have been extensively studied for certain climatic regions but very little is known on their suitability to be used under Mediterranean-type conditions nor their temporal stability, both diurnally and between seasons. Thus, the objective of this work was to determine the reference baselines for maize grown under Mediterranean conditions, as well as its diurnal and long-term stability. An experiment was conducted for 3 years in a maize breeding field, under well-watered and water-stressed irrigation treatments. The determined reference baselines for computing CWSI in maize have shown to be stable in the long term but markedly influenced by the meteorological variations between 10–17 h UTC (Coordinated Universal Time). These results indicate that several reference baselines should be used for CWSI computing throughout the abovementioned time interval. The CWSI values calculated for well-watered and water-stressed maize breeding plots using the reference baselines derived in this study were successfully correlated with other physiological indicators of plant water stress.