This paper presents a demonstration of an integrated risk assessment and site investigation for groundwater contamination through a case study, in which the geologic and hydrogeological feature of the site and the blueprint of the fossil power plant (FPP) were closely analyzed. Predictions for groundwater contamination in case of accidents were performed by groundwater modeling system (GMS) and modular three-dimensional multispecies transport model (MT3DMS). Results indicate that the studied site area presents a semi-isolated hydrogeological unit with multiplicity in stratum lithology, the main aquifers at the site are consisted of the filled karst development layer with a thickness between 6.0 and 40.0 m. The poor permeability of the vadose zone at the FPP significantly restricted the infiltration of contaminants through the vadose zone to the subsurface. The limited influence of rarely isotropic porous karstified carbonate rocks on the groundwater flow system premised the simulate scenarios of plume migration. Analysis of the present groundwater chemistry manifested that that the groundwater at the site and the local area are of the HCO₃–Ca, HCO₃, and SO₄–Ca types. A few of the water samples were contaminated by coliform bacteria and ammonia nitrogen as a result of the local cultivation. Prediction results indicate that the impact of normal construction and operation processes on the groundwater environment is negligible. However, groundwater may be partly contaminated within a certain period in the area of leakage from the diesel tanks, the industrial wastewater pool, and the cooling tower water tank in case of accidents. On a positive note, none of the plumes would reach the local sensitive areas for groundwater using. Finally, an anti-seepage scheme and a monitoring program are proposed to safeguard the groundwater protection. The integrated method of the site investigation and risk assessment used in this case study can facilitate the protection of groundwater for the construction of large-scale industrial project.