Solvents are widely used in organic synthesis. Sulfolane is a five-membered heterocyclic organosulfur sulfone (R-SO2-R’, where R/R’ is alkyl, alkenyl, or aryl) and an anthropogenic medium commonly used as industrial extractive solvent in the liquid-liquid and liquid-vapor extraction processes. Under standard conditions sulfolane is not aggressive towards steel, but at higher temperatures and in oxygen, water, or chlorides presence, it can be decomposed into some corrosive (by-)products with generation of SO2 and subsequent formation of corrosive H2SO3. This pilot-case study provides data from laboratory measurements performed in low conductivity sulfolane-based fluids using an industrial multi-electrochemical technique for reliable detection of corrosion processes. In particular, a comprehensive evaluation of the aqueous phase impact on general and localized corrosion of AISI 1010 carbon steel in sulfolane is presented. Assessment of corrosive damage was carried out using an open circuit potential method, potentiodynamic polarization curves, SEM/EDS and scanning Kelvin probe technique. It was found that an increase in the water content (1–3 vol.%) in sulfolane causes a decrease in the corrosion resistance of AISI 1010 carbon steel on both uniform and pitting corrosion due to higher conductance of the sulfolane-based fluids.