In this work, a green, stable and versatile organic-solvent-free electromembrane extraction (EME) system based on semi-interpenetrating polymer networks (semi-IPN) is proposed for the extraction and enrichment of both basic and acidic drugs from human urine. Because of its non-toxicity and high affinity in target separation, semi-solid polypropylene glycol (PPG) was selected as a component for the synthesis of semi-IPN networks via an ultrasonic-assisted blending (UAB) method. Using the homogeneous semi-IPN membrane as the supported liquid membrane (SLM), the organic-solvent-free EME system was obtained. Under the optimized conditions, the organic-solvent-free EME system showed high recovery efficiency for both basic analytes (70–97%) and acidic analytes (86–100%). Moreover, the organic-solvent-free EME set-up could be reused in eight successive extraction batches without an obvious decrease in extraction efficiency. In addition, the EME system could be conveniently stored at ambient temperature for a long time, which will greatly promote the commercialization of EME. We believe this study provides new insights and attempts in the development of green sample preparation approaches.