The subsurface Lithological and Structural framework was investigated to understand its effects on groundwater aquiferous occurrence in this study, underlined by the Precambrian Basement Complex of Nigeria, with granite, gneiss, and schist occurring as the dominant rock types. To successfully map the subsurface, fifty-two (52) Vertical Electrical Sounding points were probed to a depth of current electrode spacing of 100m depth to obtain the variation in the resistivity measurement of the underlying weathered basement and basement rock in the subsurface. Apparent resistivity values and current electrode spacing are plotted on a bi-logarithm plot and correlated to standard curves to estimate subsurface layers' depth, thickness, and resistivity values. WinResist software uses a mathematical algorithm to estimate further the geoelectric parameters to find the best-fit model that matches the observed data. Golden Surfer software was used to represent the geoelectric parameters to aid in geospatial representation. Results show 3-5 lithological layers, which include Topsoil, Clay, Laterite, Sand, Sandy Clay, and Fresh Basement with resistivity value range 82.1Ωm - 2648.2Ωm, 21.8Ωm - 98.4Ωm, 102.3Ωm -167.5Ωm, 404.6Ωm - 2468.2Ωm and 606.8Ωm - 20,535.90Ωm indicating a weathered and fresh unweathered basement rocks layers with H, KH, HA, HKH, KHKH, QH and A geophysical curve which are also typical geometry of weathered material and limited or no fractures basement rock layer. Basement rock resistivity, Overburden thickness, Reflection coefficient, longitudinal conductance, Anisotropy coefficient range (606.8Ωm-20535.9Ωm, 2.6m - 35.6m, 0.3-1.0, 0.01-0.86 and 0.7-3.3) respectively which a typical value of shallow to deep overburden layer with limited or no-detected fracture basement rock). Incorporating the geoelectric parameters value obtained and calculated reveal limited structural deformation of the basement rocks to yield fracture capable of creating secondary porosity in the area while the lithology of the weathered layers becomes the exploitable source for groundwater recovery in the study area.