This paper proposes for the first time, the use of high nitrogen doped graphene (HNDG) as a new cationic carrier for the enhancement of electromembrane extraction (EME) performance. Sensitivity of EME was improved by the modification of supported liquid membrane composition through the addition of HND-G into 1-octanol for the extraction of naproxen and sodium diclofenac asmodel acidic drugs. The comparison between HND-G-modified EME and conventional EME showed that HND-G could increase the overall partition coefficient of acidic drugs in the membrane due to the fact that HND-G acts as an ion pair reagent and there is an electrostatic interaction between positively charged HND-G and acidic drugs with negative charge. During the extraction, model acidic drugs migrated from a 10mL aqueous sample solution (pH 9.6) through a thin layer of 1-octanol containing 0.6% w/v of HND-G that was impregnated in the pores of a hollow fiber, into a 30 mu L basic aqueous acceptor solution (pH 12.3) present in the lumen of the hollow fiber. Equilibrium extraction conditions were obtained after 16 min of operation with the whole assembly agitated at 1000 rpm. Under the optimized conditions, the enrichment factors were between 238 and 322 and also the LODs ranged from 0.1 to 0.7 ng/mL in different samples. Finally, the applicability of this method was evaluated by the extraction and determination of drugs of interest in real urine samples.