Electro membrane extraction-solid-liquid phase microextraction (EME-SLPME) was developed for the first time to determine phenolic contaminants in water. The extraction system consisted of a solid/liquid interface that permitted a three-phase microextraction approach involving an aqueous sample (donor phase): an organic solvent-sorbent within a membrane bag, and an organic solvent (extractant phase), operated in a direct immersion sampling system. The sorbent, reduced graphene oxide/polyvinyl alcohol, synthesized using graphene oxide and polyvinyl alcohol by dispersing the graphene oxide in polyvinyl alcohol and chemically reducing it in aqueous solution. The prepared sorbent was dispersed in 1-octanol and the solution was immobilized by sonication in the membrane bag wall pores which was in contact with the aqueous donor solution and organic extractant solvent (1-octanol) in the main bag itself. The analytes were transported by application of an electrical potential difference of 100V across the sorbent/solvent phase from the aqueous sample into the organic extractant phase in the membrane bag. After extraction and derivatization, gas chromatography-mass spectrometry was used to determine the derivatized analytes. This proposed EME-LSPME procedure provided high extraction efficiency with relative recoveries up to 99.6%. A linearity range of between 0.05 and 100μgL(-1) with corresponding coefficients of determination (r(2)) of between 0.987 and 0.996 were obtained. The limits of detection were in the range of between 0.003 and 0.053μgL(-1). This proposed method was successfully applied to the extraction of phenolic contaminants from water sample.