Vertical electrical sounding, well inventory and physicochemical analysis were conducted to evaluate soil corrosivity and aquifer protective capacity of overburden units in the basement complex terrain of Ado-Ekiti, southwestern Nigeria. The topsoil is composed of slightly corrosive materials at the eastern, southern and northeastern flanks and the central portion with resistivity values ranging from 60 to 180 Ωm. Moderately corrosive/slightly corrosive materials (with resistivity values of 10 < ρ < 60 Ωm) constitute the second layer around the eastern, southern and north-eastern flanks. Pockets of areas in the northwestern, southeastern, eastern and central parts of the metropolis are practically non-corrosive with resistivity values in excess of 200 Ωm. Zones of good, moderate, weak and poor overburden protective capacity were delineated, with longitudinal conductance (S) values of 0.7 < S < 4.9, 0.2 < S < 0.69, 0.1 < S < 0.19 and S < 0.1 mhos, respectively. On a regional consideration, 23.31%, 18.80% and 57.9% of the study area is characterised by overburden materials of poor, weak and moderate protective capacity, respectively. Only 6.02% of the area indicates good overburden protective capacity.