Introducing new membranes with green chemistry approach seems to be a great challenge for the development of a practical method in separation science. In this regard, for the first time, polyacrylamide gel as a new membrane in electromembrane extraction (EME) was used for the extraction of three model basic drugs (pseudoephedrine (PSE), lidocaine (LID), and propranolol (PRO)), followed by HPLC-UV. In comparison with conventional EME, in this method neither organic solvent nor carrier agents were used for extraction of mentioned drugs. Different variables for fabrication of polyacrylamide gel and extraction process were evaluated. Polyacrylamide gel (containing 12% (w/v) acrylamide, and 3.0% (w/w) bisacrylamide) with 2 mm thickness at pH = 1.5 was fabricated as membrane. The drugs were extracted from aqueous samples, through a polyacrylamide gel membrane, to an aqueous acceptor phase on membrane. Under the optimized extraction conditions (Voltage: 85 V, extraction time: 28 min, acceptor phase's pH: 4.0, and donor phase's pH: 7.0) limits of quantification and detection were in the ranges of 1.0–20.0 ng mL−1 and 0.3–6.0 ng mL−1, respectively. Applying the proposed method to determine and quantify intended drugs in breast milk, and wastewater samples have revealed acceptable results.