This study highlights the groundwater hydrogeochemical characteristics and processes (hydrochemistry characteristics, ion exchange, and salinization) and quality suitability assessment for irrigation purposes from five wells in the Greenbelt area located in northwestern Al-Najaf Governorate, Iraq. The suitability of groundwater for irrigation was assessed based on the irrigation water quality index (IWQI) for thirteen parameters and groundwater quality indices such as total dissolved solids (TDS), electrical conductivity (EC), sodium adsorption ratio (SAR), soluble sodium percent (SSP), residual sodium carbonate (RSC), total hardness (TH), permeability index (PI), potential salinity (PS), Kelley’s ratio (KR), and magnesium hazard ratio (MHR). The IWQI’s average values ranged between 76–139. The results of IWQI for the first and second sampling sites showed values of 139 and 104, respectively, indicating that the groundwater was unsuitable and unsafe for irrigation. In contrast, the IWQI for the third, fourth, and fifth sites were 83, 97, and 76, respectively, indicating that the groundwater was safe and possibly used for irrigation. The EC, TDS, PS, and MHR indices were all found to be unsuitable for irrigation in all five sites, and the KR index was also found to be unsuitable for agricultural irrigation in about 80% of the sites, while it was found that the indices of SAR, SSP, RSC, PI, and TH for all sites were suitable and safe for irrigation. As a result of this study, it has been determined that groundwater in the study area is unsuitable for agricultural irrigation. For sustainable groundwater exploitation, it is advised that a continuous water-quality-monitoring program should be implemented, as well as the development of suitable management practices.