Integrated geophysical investigation involving 1D vertical electrical sounding and 2D electrical resistivity tomography was carried out in the Precambrian Basement Complex terrain of Modomo, SW Nigeria, with challenges of groundwater development. The objective was to use the geoelectric parameters to characterize the study area into groundwater potential zones that would assist the siting of productive wells/boreholes. Thin (generally 5 m, while success and failure rates of 83–100% and 57% were observed for wells/boreholes sited within partly weathered/fractured basement and fresh basement, respectively. The generated groundwater potential map rated the study area as very low (11.6%), low (51.8%), moderate (30%) and high (6.6%). Areas with moderate and high potential ratings accounted for 73% and 50% of well/borehole development success rates, respectively, while 60% and 44% failure rates characterized the very low and low groundwater potential zones. The groundwater potential map is significantly validated by the existing well/borehole yield information. This demonstrates the reliability of this technique of groundwater potential assessment in the basement complex environment with groundwater development challenges.